Catalyst composition comprising shuttling agent for ethylene copolymer formation

ABSTRACT

A composition for use in forming a multi-block copolymer from a single polymerizable monomer, said copolymer containing therein two or more segments or blocks differing in branching index, a polymerization process using the same, and the resulting polymers, wherein the composition comprises the admixture or reaction product resulting from combining: (A) a first olefin polymerization catalyst, (B) a second olefin polymerization catalyst capable of preparing polymers differing in chemical or physical properties from the polymer prepared by catalyst (A) under equivalent polymerization conditions, at least one of catalyst (A) or catalyst (B) being capable of forming a branched polymer by means of chain walking or reincorporation of in situ formed olefinic polymer chains, and (C) a chain shuttling agent.

CROSS REFERENCE STATEMENT

This application claims the benefit of U.S. Provisional Application No.60/553,906, filed Mar. 17, 2004. For purposes of United States patentpractice, the contents of this provisional application are hereinincorporated by reference.

BACKGROUND OF THE INVENTION

The present invention relates to compositions for polymerizing ethylene,to form an interpolymer product having unique physical properties, to aprocess for preparing such interpolymers, and to the resulting polymerproducts. In another aspect, the invention relates to methods of usingthese polymers in applications requiring unique combinations of physicalproperties. In still another aspect, the invention relates to thearticles prepared from these polymers. The inventive polymers comprisetwo or more differing regions or segments (blocks) causing the polymerto possess unique physical properties. These multi-block copolymers andpolymeric blends comprising the same are usefully employed in thepreparation of solid articles such as moldings, films, sheets, andfoamed objects by molding, extruding, or other processes, and are usefulas components or ingredients in adhesives, laminates, polymeric blends,and other end uses. The resulting products are used in the manufactureof components for automobiles, such as profiles, bumpers and trim parts;packaging materials; electric cable insulation, and other applications.

It has long been known that polymers containing a block-type structureoften have superior properties compared to random copolymers and blends.For example, triblock copolymers of styrene and butadiene (SBS) andhydrogenated versions of the same (SEBS) have an excellent combinationof heat resistance and elasticity. Other block copolymers are also knownin the art. Generally, block copolymers known as thermoplasticelastomers (TPE) have desirable properties due to the presence of “soft”or elastomeric block segments connecting “hard” either crystallizable orglassy blocks in the same polymer. At temperatures up to the melttemperature or glass transition temperature of the hard segments, thepolymers demonstrate elastomeric character. At higher temperatures, thepolymers become flowable, exhibiting thermoplastic behavior. Knownmethods of preparing block copolymers include anionic polymerization andcontrolled free radical polymerization. Unfortunately, these methods ofpreparing block copolymers require sequential monomer addition and batchprocessing and the types of monomers that can be usefully employed insuch methods are relatively limited. For example, in the anionicpolymerization of styrene and butadiene to form a SBS type blockcopolymer, each polymer chain requires a stoichiometric amount ofinitiator and the resulting polymers have extremely narrow molecularweight distribution, Mw/Mn, preferably from 1.0 to 1.3. Additionally,anionic and free-radical processes are relatively slow, resulting inpoor process economics.

It would be desirable to produce block copolymers catalytically, thatis, in a process wherein more than one polymer molecule is produced foreach catalyst or initiator molecule. In addition, it would be highlydesirable to produce multi-block copolymers having both highlycrystalline and amorphous blocks or segments, from a single monomer,ethylene, which is generally unsuited for use in anionic or free-radicalpolymerizations. Finally, if would be highly desirable to be able to usea continuous process for production of the present multi-blockcopolymers.

Previous researchers have stated that certain homogeneous coordinationpolymerization catalysts can be used to prepare polymers having asubstantially “block-like” structure by suppressing chain-transferduring the polymerization, for example, by conducting the polymerizationprocess in the absence of a chain transfer agent and at a sufficientlylow temperature such that chain transfer by β-hydride elimination orother chain transfer processes is essentially eliminated. Under suchconditions, the sequential addition of different monomers was said toresult in formation of polymers having sequences or segments ofdifferent monomer content. Several examples of such catalystcompositions and processes are reviewed by Coates, Hustad, and Reinartzin Angew. Chem. Int. Ed., 41, 2236-2257 (2002) as well asUS-A-2003/0114623.

The use of certain metal alkyl compounds and other compounds, such ashydrogen, as chain transfer agents to interrupt chain growth in olefinpolymerizations is well known in the art. In addition, it is known toemploy such compounds, especially aluminum alkyl compounds, asscavengers or as cocatalysts in olefin polymerizations. InMacromolecules, 33, 9192-9199 (2000) the use of certain aluminumtrialkyl compounds as chain transfer agents in combination with certainpaired zirconocene catalyst compositions resulted in polypropylenemixtures containing small quantities of polymer fractions containingboth isotactic and atactic chain segments. In Liu and Rytter,Macromolecular Rapid Comm., 22, 952-956 (2001) and Bruaseth and Rytter,Macromolecules, 36, 3026-3034 (2003) mixtures of ethylene and 1-hexenewere polymerized by a similar catalyst composition containingtrimethylaluminum chain transfer agent.

In U.S. Pat. Nos. 6,380,341 and 6,169,151, use of a “fluxional”metallocene catalyst, that is a metallocene capable of relatively facileconversion between two stereoisomeric forins having differingpolymerization characteristics such as differing reactivity ratios wassaid to result in production of olefin copolymers having a “blocky”structure from propylene.

In JACS. 2004, 126, 10701-10712, Gibson, et al discuss the effects of“catalyzed living polymerization” on molecular weight distribution. Theauthors define catalyzed living polymerization in this manner:

“. . . if chain transfer to aluminum constitutes the sole transfermechanism and the exchange of the growing polymer chain between thetransition metal and the aluminum centers is very fast and reversible,the polymer chains will appear to be growing on the aluminum centers.This can then reasonably be described as a catalyzed chain growthreaction on aluminum . . . . An attractive manifestation of this type ofchain growth reaction is a Poisson distribution of product molecularweights, as opposed to the Schulz-Flory distribution that arises whenβ-H transfer accompanies propagation.”

The authors reported the results for the catalyzed livinghomopolymerization of ethylene using an iron containing catalyst incombination with ZnEt₂, ZnMe₂, or Zn(i-Pr)₂. Homoleptic allkyls ofaluminum, boron, tin, lithium, magnesium and lead did not inducecatalyzed chain growth. Using GaMe₃ as cocatalyst resulted in productionof a polymer having a narrow molecular weight distribution. However,after analysis of time-dependent product distribution, the authorsconcluded this reaction was, “not a simple catalyzed chain growthreaction.” The reference fails to disclose the use of two or morecatalysts in combination with a chain shuttling agent to makemulti-block copolymers. Similar processes employing single catalystshave been described in U.S. Pat. Nos. 5,210,338, 5,276,220, and6,444,867.

Earlier workers have claimed to have formed block copolymers using asingle Ziegler-Natta type catalyst in multiple reactors arranged inseries, see for example U.S. Pat. Nos. 3,970,719 and 4,039,632.Additional Ziegler-Natta based processes and polymers are disclosed inU.S. Pat. Nos. 4,971,936; 5,089,573; 5,118,767; 5,118,768; 5,134,209;5,229,477; 5,270,276; 5,270,410; 5,294,581; 5,543,458; 5,550,194; and5,693,713, as well as in EP-A-470,171 and EP-A-500,530.

It is known that random defects occur in polymers prepared from singlemonomers using, for example, Ni and Pd-diimine catalysts. The catalystengages in “chain walking” during polymerization forming branchedchains, highly branched (hyper-branched), or even dendermeric branchedchains in the resulting polymer. Examples of this type of polymerizationare found in Chem. Rev., 100, 1169-1203 (2000), Macromolecular Chemistryand Physics, 205, 897-906, (2004), and elsewhere. It is also known thatlong chain branched polymer units may be prepared from ethylene usingcertain homogeneous polymerization catalysts such as 1-, and2-t-butyldimethylsiloxy substituted bis(indenyl)zirconium complexes withmetlhylalumoxane cocatalyst. Examples of this type of polymerization arefound in J. Mol. Catal. A: Chemical, 102 59-65 (1995); Macromolecules21, 617-622 (1988); J. Mol. Catal. A: Chemical, 185, 57-64 (2002), andJ. Am. Chem. Soc., 117, 6414-6415 (1995).

Despite the advances by the foregoing researchers, there remains a needin the art for a polymerization process that is capable of preparingblock like copolymers, especially multi-block copolymers, and mostespecially linear multi-block copolymers, in high yield and selectivityfrom a single monomer, ethylene, by the use of a shuttling agent. Inaddition it would be desirable to provide such an improved process thatis capable of preparing multi-block copolymers, especially linearmulti-block copolymers, having a relatively narrow molecular weightdistribution. It would further be desirable to provide an improvedprocess for preparing copolymers having more than two segments orblocks. Furthermore, it would be desirable to provide a process foridentifying combinations of catalysts and chain shuttling agents capableof making such multi-block copolymers. Even further, it would bedesirable to provide a process for independent control of the order ofthe various polymer blocks, especially a process for preparing olefinblock copolymers containing terminal blocks having high crystallinityand/or functionality from a single olefin reagent. Finally, it would bedesirable to provide an improved process for preparing any of theforegoing desirable polymer products in a continuous process, withoutrequired sequential addition of two of more monomers. Highly desirably,such process allows for independent control of the quantity and/oridentity of the shuttling agent(s) and/or catalysts used.

SUMMARY OF THE INVENTION

According to the present invention there are now provided a compositionfor use in the polymerization of ethylene to form a segmented copolymer(multi-block copolymer), said copolymer containing therein two or more,preferably three or more segments or blocks differing in one or morechemical or physical properties as further disclosed here in, thecomposition comprising the admixture or reaction product resulting fromcombining:

(A) a first olefin polymerization catalyst,

(B) a second olefin polymerization catalyst capable of preparingpolymers differing in chemical or physical properties from the polymerprepared by catalyst (A) under equivalent polymerization conditions,

at least one of catalyst (A) or catalyst (B) being capable of forming abranched polymer by means of chain walking or reincorporation of in situformed olefinic polymer chains, and

(C) a chain shuttling agent.

Preferably the admixture or reaction product results from combining:

(A) a first olefin polymerization catalyst capable of forming a highlycrystalline ethylene homopolymers by ethylene polymerization;

(B) a second olefin polymerization catalyst capable of forming abranched polymer upon polymerization by means of chain walking orreincorporation of in situ formed olefinic polymer chains, and

(C) a chain shuttling agent.

In another embodiment of the invention, there is provided a method forselecting an admixture of catalysts (A) and (B) and chain shuttlingagent (C) capable of producing multi-block copolymers according to theinvention.

In a further embodiment of the present invention there is provided aprocess for preparing a segmented copolymer, said process comprisingcontacting ethylene under addition polymerization conditions with acomposition comprising:

the admixture or reaction product resulting from combining:

(A) a first olefin polymerization catalyst,

(B) a second olefin polymerization catalyst capable of preparingpolymers differing in chemical or physical properties from the polymerprepared by catalyst (A) under equivalent polymerization conditions,

at least one of catalyst (A) or catalyst (B) being capable of forming abranched polymer by means of chain walking or reincorporation of in situformed olefinic polymer chains, and

(C) a chain shuttling agent.

Preferably, the foregoing process takes the form of a continuoussolution process for forming block copolymers, especially multi-blockcopolymers, preferably linear multi-block copolymers, using multiplecatalysts that are incapable of interconversion. That is the catalystsare chemically distinct. Under continuous solution polymerizationconditions, the process is ideally suited for polymerization of ethyleneat high monomer conversions. Under these polymerization conditions,shuttling from the chain shuttling agent to the catalyst becomesadvantaged compared to chain growth, and multi-block copolymers,especially linear multi-block copolymers according to the invention areformed in high efficiency.

In another embodiment of the invention there is provided a highmolecular weight, segmented copolymer (multi-block copolymer) preparedfrom ethylene, containing therein two or more, preferably three or moresegments differing in density or other chemical or physical property.Highly preferably the copolymer possesses a molecular weightdistribution, Mw/Mn, of less than 3.0, preferably less than 2.8.

In yet another embodiment of the invention, there are providedfunctionaslized derivatives of the foregoing segmented or multi-blockcopolymers.

In a still further embodiment of the present invention, there isprovided a polymer mixture comprising: (1) an organic or inorganicpolymer, preferably a homopolymer of ethylene or of propylene and/or acopolymer of ethylene or propylene and a copolymerizable comonomer, and(2) a high molecular weight, multi-block copolymer according to thepresent invention or prepared according to the process of the presentinvention. In a desirable embodiment component (1) is a matrix polymercomprising high density polyethylene or isotactic polypropylene andcomponent (2) is an elastomeric multi-block copolymer. In a preferredembodiment, component (2) comprises occlusions of the matrix polymerformed during compounding of components (1) and (2).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic representation of the process of polymer chainshuttling involving two catalyst sites.

DETAILED DESCRIPTION OF THE INVENTION

All references to the Periodic Table of the Elements herein shall referto the Periodic Table of the Elements, published and copyrighted by CRCPress, Inc., 2003. Also, any references to a Group or Groups shall be tothe Group or Groups reflected in this Periodic Table of the Elementsusing the IUPAC system for numbering groups. Unless stated to thecontrary, implicit from the context, or customary in the art, all partsand percents are based on weight. For purposes of United States patentpractice, the contents of any patent, patent application, or publicationreferenced herein are hereby incorporated by reference in their entirety(or the equivalent US version thereof is so incorporated by reference)especially with respect to the disclosure of synthetic techniques,definitions (to the extent not inconsistent with any definitionsprovided herein) and general knowledge in the art.

The term “comprising” and derivatives thereof is not intended to excludethe presence of any additional component, step or procedure, whether ornot the same is disclosed herein. In order to avoid any doubt, allcompositions claimed herein through use of the term “comprising” mayinclude any additional additive, adjuvant, or compound whether polymericor otherwise, unless stated to the contrary. In contrast, the term,“consisting essentially of” excludes from the scope of any succeedingrecitation any other component, step or procedure, excepting those thatare not essential to operability. The term “consisting of” excludes anycomponent, step or procedure not specifically delineated or listed. Theterm “or”, unless stated otherwise, refers to the listed membersindividually as well as in any combination.

The term “polymer”, includes both conventional homopolymers, that is,homogeneous polymers prepared from a single monomer, and copolymers(interchangeably referred to herein as interpolymers), meaning polymersprepared by reaction of at least two monomers or otherwise containingchemically differentiated segments or blocks therein even if formed froma single monomer. More specifically, the term “polyethylene” includeshomopolymers of ethylene and copolymers of ethylene and one or more C₃₋₈α-olefins in which ethylene comprises at least 50 mole percent. The term“crystalline” if employed, refers to a polymer that possesses a firstorder transition or crystalline melting point (Tm) as determined bydifferential scanning calorimetry (DSC) or equivalent technique. Theterm may be used interchangeably with the term “semicrystalline”. Theterm “amorphous” refers to a polymer lacking a crystalline meltingpoint.

The term “multi-block copolymer” or “segmented copolymer” refers to apolymer comprising two or more chemically distinct regions or segments(referred to as “blocks”) preferably joined in a linear manner, that is,a polymer comprising chemically differentiated units which are joinedend-to-end with respect to polymerized ethylenic functionality, ratherthan in pendent or grafted fashion. In a preferred embodiment, theblocks differ in the density, the amount of crystallinity, thecrystallite size attributable to a polymer of such composition, theamount of chain branching, the homogeneity, or any other chemical orphysical property attributable to an olefin polymer. Compared to blockcopolymers of the prior art, including copolymers produced by sequentialmonomer addition, fluxional catalysts, or anionic polymerizationtechniques, certain of the polymers of the invention are characterizedby unique distributions of both polymer polydispersity (PDI or Mw/Mn),block length distribution, and/or block number distribution, due, in apreferred embodiment, to the effect of the shuttling agent(s) incombination with multiple catalysts. More specifically, the polymersdesirably possess PDI from 1.7 to 2.9, preferably from 1.8 to 2.5.

Because the respective distinguishable segments or blocks are joinedinto single polymer chains, the polymer cannot be completelyfractionated using standard selective extraction techniques. Forexample, polymers containing regions that are relatively crystalline(high density segments) and regions that are relatively amorphous (lowerdensity segments) cannot be selectively extracted or fractionated usingdiffering solvents. In a preferred embodiment the quantity ofextractable polymer using either a dialkyl ether- or an alkane-solventis less than 10 percent, more preferably less than 5 percent and mostpreferably less than 2 percent of the total polymer weight.

In addition, the multi-block copolymers of the invention desirablypossess a PDI fitting a Schutz-Flory distribution rather than a Poissondistribution. The use of the present polymerization process results in aproduct having both a polydisperse block distribution as well as apolydisperse distribution of block sizes. This ultimates in theformation of polymer products having improved and distinguishablephysical properties. The theoretical benefits of a polydisperse blockdistribution have been previously modeled and discussed in Potemkin,Physical Review E (1998) 57(6), p. 6902-6912, and Dobrynin, J. Chem.Phys. (1997) 107(21), p 9234-9238.

In a further embodiment, the polymers of the invention, especially thosemade in a continuous, solution polymerization reactor, possess a mostprobable distribution of block lengths. Most preferred polymersaccording to the invention are multi-block copolymers containing 4 ormore blocks or segments including terminal blocks.

The following mathematical treatment of the resulting polymers is basedon theoretically derived parameters that are believed to apply to thepresent invented polymers and demonstrate that, especially in asteady-state, continuous, well-mixed reactor, the block lengths of theresulting polymer prepared using 2 or more catalysts will each conformto a most probable distribution, derived in the following manner,wherein p_(i) is the probability of propagation with respect to blocksequences from catalyst i. The theoretical treatment is based onstandard assumptions and methods known in the art and used in predictingthe effects of polymerization kinetics on molecular architecture,including the use of mass action reaction rate expressions that are notaffected by chain or block lengths. Such methods have been previouslydisclosed in W. H. Ray, J. Macromol. Sci. Rev. Macromol. Chem., C8, 1(1972) and A. E. Hamielec and J. F. MacGregor, “Polymer ReactionEngineering”, K. H. Reichert and W. Geisler, Eds., Hanser, Munich, 1983.In addition it is assumed that adjacent sequences formed by the samecatalyst form a single block. For catalyst i, the fraction of sequencesof length n is given by X_(i)[n], where n is an integer from 1 toinfinity representing the number of monomer units in the block.X _(i) [n]=(1−p _(i))p _(i) ^((n-1))most probable distribution of block lengths$N_{i} = \frac{1}{1 - p_{i}}$number average block length

Each catalyst has a probability of propagation (p_(i)) and forms apolymer segment having a unique average block length and distribution.In a most preferred embodiment, the probability of propagation isdefined as:$p_{i} = \frac{{Rp}\lbrack i\rbrack}{{{Rp}\lbrack i\rbrack} + {{Rt}\lbrack i\rbrack} + {{Rs}\lbrack i\rbrack} + \lbrack C_{i} \rbrack}$for  each  catalyst  i = {1, 2  …  }, where,

Rp[i]=Rate of monomer consumption by catalyst i, (moles/L),

Rt[i]=Total rate of chain transfer and termination for catalyst i,(moles/L),

Rs[i]=Rate of chain shuttling with dormant polymer to other catalysts,(moles/L), and

[C_(i)]=Concentration of catalyst i (moles/L).

Dormant polymer chains refers to polymer chains that are attached to aCSA.

The overall monomer consumption or polymer propagation rate, Rp[i], isdefined using an apparent rate constant, $\overset{\_}{k_{pi}},$multiplied by a total monomer concentration, [M], as follows:${{Rp}\lbrack i\rbrack} = {\theta{{\overset{\_}{k_{pi}}\lbrack M\rbrack}\lbrack C_{i} \rbrack}}$

The total chain transfer rate is given below including values for chaintransfer to hydrogen (H₂), beta hydride elimination, and chain transferto chain shuttling agent (CSA). The reactor residence time is given by θand each subscripted k value is a rate constant.Rt[i]=θ k _(H2i)[H₂][C_(i) ]+θ k _(βi)[C_(i) ]+θ k _(ai)[CSA][C _(i)]

For a dual catalyst system, the rate of chain shuttling of polymerbetween catalysts 1 and 2 is given as follows:Rs[1]=Rs[2]=θ k_(a1)[CSA]θ k_(a2)[C₁][C₂].

If more than 2 catalysts are employed then added terms and complexity inthe theoretical relation for Rs[i] result, but the ultimate conclusionthat the resulting block length distributions are most probable isunaffected.

As used herein with respect to a chemical compound, unless specificallyindicated otherwise, the singular includes all isomeric forms and viceversa (for example, “hexane”, includes all isomers of hexaneindividually or collectively). The terms “compound” and “complex” areused interchangeably herein to refer to organic-, inorganic- andorganometal compounds. The term, “atom” refers to the smallestconstituent of an element regardless of ionic state, that is, whether ornot the same bears a charge or partial charge or is bonded to anotheratom. The term “heteroatom” refers to an atom other than carbon orhydrogen. Preferred heteroatoms include: F, Cl, Br, N, O, P, B, S, Si,Sb, Al, Sn, As, Se and Ge. The term “amorphous” refers to a polymerlacking a crystalline melting point as determined by differentialscanning calorimetry (DSC) or equivalent technique.

The term, “hydrocarbyl” refers to univalent substituents containing onlyhydrogen and carbon atoms, including branched or unbranched, saturatedor unsaturated, cyclic, polycyclic or noncyclic species. Examplesinclude alkyl-, cycloalkyl-, alkenyl-, alkadienyl-, cycloalkenyl-,cycloalkadienyl-, aryl-, and alkynyl-groups. “Substituted hydrocarbyl”refers to a hydrocarbyl group that is substituted with one or morenonhydrocarbyl substituent groups. The terms, “heteroatom containinghydrocarbyl” or “heterohydrocarbyl” refer to univalent groups in whichat least one atom other than hydrogen or carbon is present along withone or more carbon atom and one or more hydrogen atoms. The term“heterocarbyl” refers to groups containing one or more carbon atoms andone or more heteroatoms and no hydrogen atoms. The bond between thecarbon atom and any heteroatom as well as the bonds between any twoheteroatoms, may be a single or multiple covalent bond or a coordinatingor other donative bond. Thus, an alkyl group substituted with aheterocycloalkyl-, aryl-substituted heterocycloalkyl-, heteroaryl-,alkyl-substituted heteroaryl-, alkoxy-, aryloxy-, dihydrocarbylboryl-,dihydrocarbylphosphino-, dihydrocarbylamino-, trihydrocarbylsilyl-,hydrocarbylthio-, or hydrocarbylseleno-group is within the scope of theterm heteroalkyl. Examples of suitable heteroalkyl groups includecyanomethyl-, benzoylmethyl-, (2-pyridyl)methyl-, andtrifluoromethyl-groups.

As used herein the term “aromatic” refers to a polyatomic, cyclic,conjugated ring system containing (4δ+2) π-electrons, wherein δ is aninteger greater than or equal to 1. The term “fused” as used herein withrespect to a ring system containing two or more polyatomic, cyclic ringsmeans that with respect to at least two rings thereof, at least one pairof adjacent atoms is included in both rings. The term “aryl” refers to amonovalent aromatic substituent which may be a single aromatic ring ormultiple aromatic rings which are fused together, linked covalently, orlinked to a common group such as a methylene or ethylene moiety.Examples of aromatic ring(s) include phenyl, naphthyl, anthracenyl, andbiphenyl, among others.

“Substituted aryl” refers to an aryl group in which one or more hydrogenatoms bound to any carbon is replaced by one or more functional groupssuch as alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heterocycloalkyl, substituted heterocycloalkyl, halogen, alkylhalos(e.g., CF₃), hydroxy, amino, phosphido, alkoxy, amino, thio, nitro, andboth saturated and unsaturated cyclic hydrocarbons which are fused tothe aromatic ring(s), linked covalently or linked to a common group suchas a methylene or ethylene moiety. The common linking group may also bea carbonyl as in benzophenone or oxygen as in diphenylether or nitrogenin diphenylamine.

The term, “branching index”, refers to the percent branched polymercontaining segments in a polymer prepared under representative ethylenepolymerization conditions by the catalyst under consideration in theabsence of other polymerization catalysts, ideally under steady-state,continuous solution polymerization conditions in a hydrocarbon diluentat 100° C., 4.5 MPa reactor pressure, and greater than 92 percent,preferably greater than 95 percent ethylene conversion. The selection ofmetal complexes or catalyst compositions having the greatest differencein branching indices results in multi-block copolymers having thelargest difference in block or segment properties, such as density.

The branching index for polymers formed from catalysts capable of chainwalking may be determined directly, for example by the use of NMRspectroscopic techniques, since linear, high density polyethylene isnormally produced by catalysts that are incapable of chain walkingpolymerization.

Monomers

The present invention results by polymerization of a single monomer,ethylene, as previously explained. In addition, it is understood by theskilled artisan that one or more addition polymerizable comonomers maybe present during the present polymerization without departing from thescope of the present invention, so long as the objects stated herein areattained. Preferably, however, the present invention takes place in thesubstantial absence of any comonomer, and most preferably the onlyolefin monomer employed in the process is ethylene.

Chain Shuttling Agents

The term, “shuttling agent” refers to a compound or mixture of compoundsemployed in the composition of the present invention that is capable ofcausing polymeryl exchange between at least two active catalyst sites ofthe catalysts included in the composition under the conditions of thepolymerization. That is, transfer of a polymer fragment occurs both toand from one or more of the active catalyst sites. In contrast to ashuttling agent, a “chain transfer agent” causes termination of polymerchain growth and amounts to a one-time transfer of growing polymer fromthe catalyst to the transfer agent. Preferably, the shuttling agent hasan activity ratio R_(A-B)/R_(B-A) of from 0.01 and 100, more preferablyfrom 0.1 to 10, most preferably from 0.5 to 2.0, and most highlypreferably from 0.8 to 1.2, wherein R_(A-B) is the rate of polymeryltransfer from catalyst A active site to catalyst B active site via theshuttling agent, and R_(B-A) is the rate of reverse polymeryl transfer,i.e., the rate of exchange starting from the catalyst B active site tocatalyst A active site via the shuttling agent. Desirably, theintermediate formed between the shuttling agent and the polymeryl chainis sufficiently stable that chain termination is relatively rare.Desirably, less than 90 percent, preferably less than 75 percent, morepreferably less than 50 percent and most desirably less than 10 percentof shuttle-polymeryl products are terminated prior to attaining 3distinguishable polymer segments or blocks. Ideally, the rate of chainshuttling (defined by the time required to transfer a polymer chain froma catalyst site to the chain shuttling agent and then back to a catalystsite) is equivalent to or faster than the rate of polymer termination,even up to 10 or even 100 times faster than the rate of polymertermination. This permits polymer block formation on the same time scaleas polymer propagation.

By selecting different combinations of catalysts having differingbranching indices as well as differing reactivities, and by pairingvarious shuttling agents or mixtures of agents with these catalystcombinations, polymer products having segments of different densities orbranching indices, different block lengths, and different numbers ofsuch segments or blocks in each copolymer can be prepared. For example,if the activity of the shuttling agent is low relative to the catalystpolymer chain propagation rate of one or more of the catalysts, longerblock length multi-block copolymers and polymer blends may be obtained.Contrariwise, if shuttling is very fast relative to polymer chainpropagation, a copolymer having a more random chain structure andshorter block lengths is obtained. An extremely fast shuttling agent mayproduce a multi-block copolymer having substantially random copolymerproperties. By proper selection of both catalyst mixture and shuttlingagent, relatively pure block copolymers, copolymers containingrelatively large polymer segments or blocks, and/or blends of theforegoing with various ethylene polymers can be obtained.

A suitable composition comprising Catalyst A, Catalyst B, and a chainshuttling agent can be selected for this invention by the followingmulti-step procedure specially adapted for block differentiation basedon branching index:

I. Ethylene is polymerized using a mixture comprising a potentialcatalyst and a potential chain shuttling agent. This polymerization testis desirably performed using a batch or semi-batch reactor (that is,without resupply of catalyst or shuttling agent), preferably withrelatively constant ethylene concentration, operating under solutionpolymerization conditions, typically using a molar ratio of catalyst tochain shuttling agent from 1:5 to 1:500. After forming a suitablequantity of polymer, the reaction is terminated by addition of acatalyst poison and the polymer's properties (branching index, Mw, Mn,and Mw/Mn or PDI) measured.

II. The foregoing polymerization and polymer testing are repeated forseveral different reaction times, providing a series of polymers havinga range of yields and PDI values.

III. Catalyst/shuttling agent pairs demonstrating significant polymertransfer both to and from the shuttling agent are characterized by apolymer series wherein the minimum PDI is less than 2.0, more preferablyless than 1.5, and most preferably less than 1.3. Furthermore, if chainshuttling is occurring, the Mn of the polymer will increase, preferablynearly linearly, as conversion is increased. Most preferredcatalyst/shuttling agent pairs are those giving polymer Mn as a functionof conversion (or polymer yield) fitting a line with a statisticalprecision (R²) of greater than 0.95, preferably greater than 0.99.

Steps I-III are then carried out for one or more additional pairings ofpotential catalysts and/or putative shuttling agents.

A suitable composition comprising Catalyst A, Catalyst B, and one ormore chain shuttling agents according to the invention is then selectedsuch that the two catalysts each undergo chain shuttling with one ormore of the chain shuttling agents, and one of the catalysts (designatedas catalyst (B), forms polymer having a higher branching index comparedto Catalyst A under the reaction conditions chosen. Most preferably, atleast one of the chain shuttling agents undergoes polymer transfer inboth the forward and reverse directions (as identified in the foregoingtest) with both Catalyst A and Catalyst B. In addition, it is preferablethat the chain shuttling agent does not reduce the catalyst activity(measured in weight of polymer produced per weight of catalyst per unittime) of either catalyst (compared to activity in the absence of ashuttling agent) by more than 60 percent, more preferably such catalystactivity is not reduced by more than 20 percent. Highly desirably,catalyst activity of at least one of the catalysts is actually increasedin the presence of the chain shuttling agent.

Alternatively, it is also possible to detect desirablecatalyst/shuttling agent pairs by performing a series of ethylenepolymerizations under standard batch reaction conditions and measuringthe resulting number average molecular weights, PDI, branching index,and polymer yield or production rate. Suitable shuttling agents arecharacterized by lowering of the resultant Mn without significantbroadening of PDI or loss of activity (reduction in yield or rate).

The foregoing tests are readily adapted to rapid throughput screeningtechniques using automated reactors and analytic probes and to formationof polymer blocks having different distinguishing properties. Forexample, a number of potential shuttling agent candidates can bepre-identified or synthesized in situ by combination of variousorganometal compounds with various proton sources and the compound orreaction product added to a polymerization reaction employing an olefinpolymerization catalyst composition. Several polymerizations areconducted at varying molar ratios of shuttling agent to catalyst. As aminimum requirement, suitable shuttling agents are those that produce aminimum PDI of less than 2.0 in variable yield experiments as describedabove, while not significantly adversely affecting catalyst activity,and preferably improving catalyst activity, as above described.

Regardless of the method for identifying, a priori, a shuttling agent,the term is meant to refer to a compound that is capable of preparingthe presently identified multi-block copolymers or usefully employedunder the polymerization conditions herein disclosed. Highly desirably,multi-block copolymers having an average number of blocks or segmentsper average chain (as defined as the average number of blocks ofdifferent composition divided by the Mn of the polymer) greater than 3.0more preferably greater than 3.5, even more preferably greater than 4.0,and less than 25, preferably less than 15, more preferably less than10.0, most preferably less than 8.0 are formed according to theinvention.

Suitable shuttling agents for use herein include Group 1, 2, 12 or 13metal compounds or complexes containing at least one C₁₋₂₀ hydrocarbylgroup, preferably hydrocarbyl substituted aluminum, gallium or zinccompounds containing from 1 to 12 carbons in each hydrocarbyl group, andreaction products thereof with a proton source. Preferred hydrocarbylgroups are allkyl groups, preferably linear or branched, C₂₋₈ alkylgroups. Most preferred shuttling agents for use in the present inventionare trialkyl aluminum and dialkyl zinc compounds, especiallytriethylaluminum, tri(i-propyl) aluminum, tri(i-butyl)aluminum,tri(n-hexyl)aluminum, tri(n-octyl)aluminum, triethylgallium, ordiethylzinc. Additional suitable shuttling agents include the reactionproduct or mixture formed by combining the foregoing organometalcompound, preferably a tri(C₁₋₈) alkyl aluminum or di(C₁₋₈) alkyl zinccompound, especially triethylaluminum, tri(i-propyl) aluminum,tri(i-butyl)aluminum, tri(n-hexyl)aluminum, tri(n-octyl)aluminum, ordiethylzinc, with less than a stoichiometric quantity (relative to thenumber of hydrocarbyl groups) of a secondary amine or a hydroxylcompound, especially bis(trimethylsilyl)amnine,t-butyl(dimethyl)siloxane, 2-hydroxymethylpyridine, di(n-pentyl)amine,2,6-di(t-butyl)phenol, ethyl(1-naphthyl)amine,bis(2,3,6,7-dibenzo-1-azacycloheptaneamine), or 2,6-diphenylphenol.Desirably, sufficient amine or hydroxyl reagent is used such that onehydrocarbyl group remains per metal atom. The primary reaction productsof the foregoing combinations most desired for use in the presentinvention as shuttling agents are n-octylaluminumdi(bis(trimethylsilyl)amide), i-propylaluminumbis(dimethyl(t-butyl)siloxide), and n-octylaluminumdi(pyridinyl-2-methoxide), i-butylaluminumbis(dimethyl(t-butyl)siloxane), i-butylaluminumbis(di(trimethylsilyl)aamide), n-octylaluminum di(pyridine-2-methoxide),i-butylaluminum bis(di(n-pentyl)amide), n-octylaluminumbis(2,6-di-t-butylphenoxide), n-octylaluminumdi(ethyl(1-naphthyl)amide), ethylaluminum bis(t-butyldimethylsiloxide),ethylaluminum di(bis(trimethylsilyl)amide), ethylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptanieamide), n-octylaluminumbis(dimethyl(t-butyl)siloxide, ethylzinc (2,6-diphenylphenoxide), andethylzinc (t-butoxide).

It will be appreciated by the skilled artisan that a suitable shuttlingagent for one catalyst or catalyst combination may not necessarily be asgood or even satisfactory for use with a different catalyst or catalystcombination. Some potential shuttling agents may adversely affect theperformance of one or more catalysts and may be undesirable for use forthat reason as well. Accordingly, the activity of the chain shuttlingagent desirably is balanced with the catalytic activity of the catalyststo achieve the desired polymer properties. In some embodiments of theinvention, best results may be obtained by use of shuttling agentshaving a chain shuttling activity (as measured by a rate of chaintransfer) that is less than the maximum possible rate.

Generally however, preferred shuttling agents possess the highest ratesof polymer transfer as well as the highest transfer efficiencies(reduced incidences of chain termination). Such shuttling agents may beused in reduced concentrations and still achieve the desired degree ofshuttling. In addition, such shuttling agents result in production ofthe shortest possible polymer block lengths. Highly desirably, chainshuttling agents with a single exchange site are employed due to thefact that the effective molecular weight of the polymer in the reactoris lowered, thereby reducing viscosity of the reaction mixture andconsequently reducing operating costs.

Catalysts

Suitable catalysts for use herein include any compound or combination ofcompounds that is adapted for preparing polymers of the desiredcomposition or type. Both heterogeneous and homogeneous catalysts may beemployed. Examples of heterogeneous catalysts include the well knownZiegler-Natta compositions, especially Group 4 metal halides supportedon Group 2 metal halides or mixed halides and alkoxides and the wellknown chromium or vanadium based catalysts. Preferably however, for easeof use and for production of narrow molecular weight polymer segments insolution, the catalysts for use herein are homogeneous catalystscomprising a relatively pure organometallic compound or metal complex,especially compounds or complexes based oil metals selected from Groups3-10 or the Lanthanide series of the Periodic Table of the Elements. Itis preferred that any catalyst employed herein, not significantlydetrimentally affect the performance of the other catalyst under theconditions of the present polymerization. Desirably, no catalyst isreduced in activity by greater than 25 percent, more preferably greaterthan 10 percent under the conditions of the present polymerization.

Metal complexes for use herein as Catalyst A include complexes oftransition metals selected from Groups 3 to 15 of the Periodic Table ofthe Elements containing one or more delocalized, π-bonded ligands orpolyvalent Lewis base ligands. Examples include metallocene,half-metallocene, constrained geometry, and polyvalent pyridylamine, orother polychelating base complexes. The complexes are genericallydepicted by the formula: MK_(k)X_(x)Z_(z), or a dimer thereof, wherein

M is a metal selected from Groups 3-15, preferably 3-10, more preferably4-8, and most preferably Group 4 of the Periodic Table of the Elements;

K independently each occurrence is a group containing delocalizedπ-electrons or one or more electron pairs through which K is bound to M,said K group containing up to 50 atoms not counting hydrogen atoms,optionally two or more K groups may be joined together forming a bridgedstructure, and further optionally one or more K groups may be bound toZ, to X or to both Z and X;

X independently each occurrence is a monovalent, anionic moiety havingup to 40 non-hydrogen atoms, optionally one or more X groups may bebonded together thereby forming a divalent or polyvalent anionic group,and, further optionally, one or more X groups and one or more Z groupsmay be bonded together thereby forming a moiety that is both covalentlybound to M and coordinated thereto;

Z independently each occurrence is a neutral, Lewis base donor ligand ofup to 50 non-hydrogen atoms containing at least one unshared electronpair through which Z is coordinated to M;

k is an integer from 0 to 3;

x is an integer from 1 to 4;

z is a number from 0 to 3; and

the sum, k+x, is equal to the formal oxidation state of M.

Suitable metal complexes include those containing from 1 to 3 π-bondedanionic or neutral ligand groups, which may be cyclic or non-cyclicdelocalized π-bonded anionic ligand groups. Exemplary of such π-bondedgroups are conjugated or nonconjugated, cyclic or non-cyclic diene anddienyl groups, allyl groups, boratabenzene groups, phosphole, and arenegroups. By the term “π-bonded” is meant that the ligand group is bondedto the transition metal by a sharing of electrons from a partiallydelocalized π-bonded.

Each atom in the delocalized π-bonded group may independently besubstituted with a radical selected from the group consisting ofhydrogen, halogen, hydrocarbyl, halohydrocarbyl, hydrocarbyl-substitutedheteroatoms wherein the heteroatom is selected from Group 14-16 of thePeriodic Table of the Elements, and such hydrocarbyl-substitutedheteroatom radicals further substituted with a Group 15 or 16 heteroatom containing moiety. In addition two or more such radicals maytogether form a fused ring system, including partially or fullyhydrogenated fused ring systems, or they may form a metallocycle withthe metal. Included within the term “hydrocarbyl” are C₁₋₂₀ straight,branched and cyclic alkyl radicals, C₆₋₂₀ aromatic radicals, C₇₋₂₀alkyl-substituted aromatic radicals, and C₇₋₂₀ aryl-substituted alkylradicals. Suitable hydrocarbyl-substituted heteroatom radicals includemono-, di- and tri-substituted radicals of boron, silicon, germanium,nitrogen, phosphorus or oxygen wherein each of the hydrocarbyl groupscontains from 1 to 20 carbon atoms. Examples include N,N-dimethylamino,pyrrolidinyl, trimethylsilyl, triethylsilyl, t-butyldimethylsilyl,methyldi(t-butyl)silyl, triphenylgermyl, and trimethylgermyl groups.Examples of Group 15 or 16 hetero atom containing moieties includeamino, phosphino, alkoxy, or alkylthio moieties or divalent derivativesthereof, for example, amide, phosphide, alkyleneoxy or alkylenethiogroups bonded to the transition metal or Lanthanide metal, and bonded tothe hydrocarbyl group, π-bonded group, or hydrocarbyl-substitutedheteroatom.

Examples of suitable anionic, delocalized π-bonded groups includecyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl,tetrahydrofluorenyl, octahydrofluorenyl, pentadieryl, cyclohexadienyl,dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl groups,phosphole, and boratabenzyl groups, as well as inertly substitutedderivatives thereof, especially C₁₋₁₀ hydrocarbyl-substituted ortris(C₁₋₁₀ hydrocarbyl)silyl-substituted derivatives thereof. Preferredanionic delocalized π-bonded groups are cyclopentadienyl,pentamethylcyclopentadienyl, tetramethylcyclopentadienyl,tetramethylsilylcyclopentadienyl, indenyl, 2,3-dimethylindenyl,fluorenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl,tetrahydrofluorenyl, octahydrofluorenyl, 1-indacenyl,3-pyrrolidinoinden-1-yl, 3,4-(cyclopenta(l)phenanthren-1-yl, andtetrahydroin denyl.

The boratabenzenyl ligands are ainionic ligands which are boroncontaining analogues to benzene. They are previously known in the arthaving been described by G. Herberich, et al., in Organometallics, 14,1, 471-480 (1995). Preferred boratabenzenyl ligands correspond to theformula:

wherein R¹ is an inert substituent, preferably selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, halo or germyl, said R¹having up to 20 atoms not counting hydrogen, and optionally two adjacentR¹ groups may be joined together. In complexes involving divalentderivatives of such delocalized π-bonded groups one atom thereof isbonded by means of a covalent bond or a covalently bonded divalent groupto another atom of the complex thereby forming a bridged system.

Phospholes are anionic ligands that are phosphorus containing analoguesto a cyclopentadienyl group. They are previously known in the art havingbeen described by WO 98/50392, and elsewhere. Preferred phospholeligands correspond to the formula:

wherein R¹ is as previously defined.

Preferred transition metal complexes for use herein correspond to theformula: MK_(k)X_(x)Z_(z), or a dimer thereof, wherein:

M is a Group 4 metal;

K is a group containing delocalized π-electrons through which K is boundto M, said K group containing up to 50 atoms not counting hydrogenatoms, optionally two K groups may be joined together forming a bridgedstructure, and further optionally one K may be bound to X or Z;

X each occurrence is a monovalent, anionic moiety having up to 40non-hydrogen atoms, optionally one or more X and one or more K groupsare bonded together to form a metallocycle, and further optionally oneor more X and one or more Z groups are bonded together thereby forming amoiety that is both covalently bound to M and coordinated thereto;

Z independently each occurrence is a neutral, Lewis base donor ligand ofup to 50 non-hydrogen atoms containing at least one unshared electronpair through which Z is coordinated to M;

k is an integer from 0 to 3;

x is an integer from 1 to 4;

z is a number from 0 to 3; and

the sum, k+x, is equal to the formal oxidation state of M.

Preferred complexes include those containing either one or two K groups.The latter complexes include those containing a bridging group linkingthe two K groups. Preferred bridging groups are those corresponding tothe formula (ER′₂)_(e) wherein E is silicon, germanium, tin, or carbon,R′ independently each occurrence is hydrogen or a group selected fromsilyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, said R′having up to 30 carbon or silicon atoms, and e is 1 to 8. Preferably, R′independently each occurrence is methyl, ethyl, propyl, benzyl,tert-butyl, phenyl, methoxy, ethoxy or phenoxy.

Examples of the complexes containing two K groups are compoundscorresponding to the formula:

wherein:

M is titanium, zirconium or hafnium, preferably zirconium or hafnium, inthe +2 or +4 formal oxidation state;

R³ in each occurrence independently is selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo andcombinations thereof, said R³ having up to 20 non-hydrogen atoms, oradjacent R³ groups together form a divalent derivative (that is, ahydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fusedring system, and

X″ independently each occurrence is an anionic ligand group of up to 40non-hydrogen atoms, or two X″ groups together form a divalent anionicligand group of up to 40 non-hydrogen atoms or together are a conjugateddiene having from 4 to 30 non-hydrogen atoms bound by means ofdelocalized π-electrons to M, whereupon M is in the +2 formal oxidationstate, and

R′, E and e are as previously defined.

Exemplary bridged ligands containing two π-bonded groups are:dimethylbis(cyclopentadienyl)silane,dimethylbis(tetramethylcyclopentadienyl)silane,dimethylbis(2-ethylcyclopentadien-1-yl)silane,dimethylbis(2-t-butylcyclopeentadien-1-yl)silane,2,2-bis(tetramethylcyclopentadienyl)propane,dimethylbis(inden-1-yl)silane, dimethylbis(tetrahydroinden-1-yl)silane,dimethylbis(fluoren-1-yl)silane,dimethylbis(tetrahydrofluoren-1-yl)silane,dimethylbis(2-methyl-4-phenylinden-1-yl)-silane,dimethylbis(2-methylinden-1-yl)silane,dimethyl(cyclopentadienyl)(fluoren-1-yl)silane,dimethyl(cyclopentadienyl)(octahydrofluoren-1-yl)silane,dimethyl(cyclopentadienyl)(tetrahydrofluoren-1-yl)silane,(1,1,2,2-tetramethy)-1,2-bis(cyclopentadienyl)disilane,(1,2-bis(cyclopentadienyl)ethane, anddimethyl(cyclopentadienyl)-1-(fluoren-1-yl)methane.

Preferred X″ groups are selected from hydride, hydrocarbyl, silyl,germyl, halohydrocarbyl, halosilyl, silylhydrocarbyl andaminohydrocarbyl groups, or two X″ groups together form a divalentderivative of a conjugated diene or else together they form a neutral,π-bonded, conjugated diene. Most preferred X″ groups are C₁₋₂₀hydrocarbyl groups.

Examples of metal complexes of the foregoing formula suitable for use inthe present invention include:

bis(cyclopentadienyl)zirconiumdimethyl, bis(cyclopentadienyl)zirconiumdibenzyl, bis(cyclopentadienyl)zirconium methyl benzyl,bis(cyclopentadienyl)zirconium methyl phenyl,bis(cyclopentadienyl)zirconiumdiphenyl,bis(cyclopentadienyl)titanium-allyl,bis(cyclopentadienyl)zirconiummethylmethoxide,bis(cyclopentadienyl)zirconiummethylchloride,bis(pentamethylcyclopentadienyl)zirconiumdimethyl,bis(pentamethylcyclopentadienyl)titaniumdimethyl,bis(indenyl)zirconiumdimethyl, indenylfluorenylzirconiumdimethyl,bis(indenyl)zirconiummethyl(2-(dimethylainino)benzyl),bis(indenyl)zirconiummethyltrimethylsilyl,bis(tetrahydroindenyl)zirconiummetliyltrimethylsilyl,bis(pentamethylcyclopentadienyl)zirconiummethylbenzyl,bis(pentamethylcyclopentadienyl)zirconiumdibenzyl,bis(pentamethylcyclopentadienyl)zirconiummethylmethoxide,bis(pentamethylcyclopentadienyl)zirconiummethylchloride,bis(methylethylcyclopentadienyl)zirconiumdimethyl,bis(butylcyclopentadienyl)zirconiumdibenzyl,bis(t-butylcyclopentadienyl)zirconiumdimethyl,bis(ethyltetramethylcyclopentadienyl)zirconiumdimethyl,bis(methylpropylcyclopentadienyl)zirconiumdibenzyl,bis(trimethylsilylcyclopentadienyl)zirconiumdibenzyl,dimethylsilylbis(cyclopentadienyl)zirconiumdichloride,dimethylsilylbis(cyclopentadienyl)zirconiumdimethyl,dimethylsilylbis(tetramethylcyclopentadienyl)titanium (III) allyldimethylsilylbis(t-butylcyclopelntadienyl)zirconiumdichloride,dimethylsilylbis(n-butylcyclopentadienyl)zirconiumdichloride,(dimethylsilylbis(tetramethylcyclopentadienyl)titanium(III)2-(dimethylamino)benzyl,(dimethylsilylbis(n-butylcyclopentadienyl)titanium(III)2-(dimethylamino)benzyl, dimethylsilylbis(indenyl)zirconiumdichloride,dimethylsilylbis(indenyl)zirconiumdimetliyl,dimethylsilylbis(2-methylindenyl)zirconiumdimethyl,dimethylsilylbis(2-methyl-4-phenylindenyl)zirconiumdimethyl,dimethylsilylbis(2-methylindenyl)zirconium-1,4-diphenyl-1,3-butadiene,dimethylsilylbis(2-metlyl-4-phelnylindenyl)zirconium (II)1,4-diphenyl-1,3-butadiene,dimethylsilylbis(4,5,6,7-tetrahydroinden-1-yl)zirconiumdichloride,dimethylsilylbis(4,5,6,7-tetrahydroinden-1-yl)zirconiumdimethyl,dimethylsilylbis(tetrahydroindenyl)zirconium(II)1,4-diphenyl-1,3-butadiene,dimethylsilylbis(tetramethylcyclopentadienyl)zirconium dimethyldimethylsilylbis(fluorenyl)zirconiumdimethyl,dimethylsilylbis(tetrahydrofluorenyl)zirconium bis(trimethylsilyl),ethylenebis(indenyl)zirconiumdichloride,ethylenebis(indenyl)zirconiumdimethyl,ethylenebis(4,5,6,7-tetrahydroindenyl)zirconiumdichloride,ethylenebis(4,5,6,7-tetrahydroindenyl)zirconiumdimethyl,(isopropylidene)(cyclopentadienyl)(fluorenyl)zirconitumdibenzyl, anddimethylsilyl(tetrametlhylcyclopentadieniyl)(fluorenyl)zirconiumdimethyl.

A further class of metal complexes utilized in the present inventioncorresponds to the preceding formula: MKZ_(z)X_(x), or a dimer thereof,wherein M, K, X, x and z are as previously defined, and Z is asubstituent of up to 50 non-hydrogen atoms that together with K forms ametallocycle with M.

Preferred Z substituents include groups containing up to 30 non-hydrogenatoms comprising at least one atom that is oxygen, sulfur, boron or amember of Group 14 of the Periodic Table of the Elements directlyattached to K, and a different atom, selected from the group consistingof nitrogen, phosphorus, oxygen or sulfur that is covalently bonded toM.

More specifically this class of Group 4 metal complexes used accordingto the present invention includes “constrained geometry catalysts”corresponding to the formula:

wherein:

M is titanium or zirconium, preferably titanium in the +2, +3, or +4formal oxidation state;

K¹ is a delocalized, π-bonded ligand group optionally substituted withfrom 1 to 5 R² groups,

R² in each occurrence independently is selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo andcombinations thereof, said R² having up to 20 non-hydrogen atoms, oradjacent R² groups together form a divalent derivative (that is, ahydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fusedring system,

each X is a halo, hydrocarbyl, hydrocarbyloxy or silyl group, said grouphaving up to 20 non-hydrogen atoms, or two X groups together form aneutral C₅₋₃₀ conjugated diene or a divalent derivative thereof;

x is 1 or 2;

Y is —O—, —S—, —NR′—, —PR′—; and

X′ is SiR′₂, CR′₂, SiR′₂SiR′₂, CR′₂CR′₂, CR′═CR′, CR′₂SiR′₂, or GeR′₂,wherein

R′ independently each occurrence is hydrogen or a group selected fromsilyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, said R′having up to 30 carbon or silicon atoms.

Specific examples of the foregoing constrained geometry metal complexesinclude compounds corresponding to the formula:

wherein,

Ar is an aryl group of from 6 to 30 atoms not counting hydrogen;

R⁴ independently each occurrence is hydrogen, Ar, or a group other thanAr selected from hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylgermyl,halide, hydrocarbyloxy, trihydrocarbylsiloxy,bis(trihydrocarbylsilyl)amino, di(hydrocarbyl)amino,hydrocarbadiylamino, hydrocarbylimino, di(hydrocarbyl)phosphino,hydrocarbadiylphosphino, hydrocarbylsulfido, halo-substitutedhydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, trihydrocarbylsilyl-substituted hydrocarbyl, trihydrocarbylsiloxy-substitutedhydrocarbyl, bis(trihydrocarbylsilyl)amino-substituted hydrocarbyl,di(hydrocarbyl)amino-substituted hydrocarbyl,hydrocaxbyleneamino-substituted hydrocarbyl,di(hydrocarbyl)phosphino-substituted hydrocarbyl,hydrocarbylenephosphino-substituted hydrocarbyl, orhydrocarbylsulfido-substituted hydrocarbyl, said R group having up to 40atoms not counting hydrogen atoms, and optionally two adjacent R⁴ groupsmay be joined together forming a polycyclic fused ring group;

M is titanium;

X′ is SiR⁶ ₂, CR⁶ ₂, SiR⁶ ₂SiR⁶ ₂, CR⁶ ₂CR⁶ ₂, CR⁶═CR⁶, CR⁶ ₂SiR⁶ ₂,BR⁶, BR⁶L″, or GeR⁶ ₂;

Y is —O—, —S—, —NR⁵—, —PR⁵—; —NR⁵ ₂, or —PR⁵ ₂;

R⁵, independently each occurrence, is hydrocarbyl, trihydrocarbylsilyl,or trihydrocarbylsilylhydrocarbyl, said R⁵ having up to 20 atoms otherthan hydrogen, and optionally two R⁵ groups or R⁵ together with Y or Zform a ring system;

R⁶, independently each occurrence, is hydrogen, or a member selectedfrom hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenatedaryl, —NR⁵ ₂, and combinations thereof, said R⁶ having up to 20non-hydrogen atoms, and optionally, two R⁶ groups or R⁶ together with Zforms a ring system;

Z is a neutral diene or a monodentate or polydentate Lewis baseoptionally bonded to R⁵, R⁶, or X;

X is hydrogen, a monovalent anionic ligand group having up to 60 atomsnot counting hydrogen, or two X groups are joined together therebyforming a divalent ligand group;

x is 1 or 2; and

z is 0, 1 or 2.

Preferred examples of the foregoing metal complexes are substituted atboth the 3- and 4-positions of a cyclopentadienyl or indenyl group withan Ar group.

Examples of the foregoing metal complexes include:

-   (3-phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3-phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,3-diphenyl-1,3-butadiene;-   (3-(pyrrol-1-yl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3-(pyrrol-1-yl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-(pyrrol-1-yl)cyclopentadien-1-yl))dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   (3-(1-methylpyrrol-3-yl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3-(1-metlhylpyrrol-3-yl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-(1-methylpyrrol-3-yl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   (3,4-diphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3,4-diphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3,4-diphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,3-pentadiene;-   (3-(3-N,N-dimethylamino)phenyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3-(3-N,N-dimethylamino)phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-(3-N,N-dimethylamino)phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   (3-(4-methoxyphenyl)-4-methylcyclopentadien-1-yl)dimethyl(t-butylarnido)silanetitanium    dichloride,-   (3-(4-methoxyphenyl)-4-phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-4-methoxyphenyl)-4-phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   (3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   (3-phenyl-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3-phenyl-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-phenyl-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   2-methyl-(3,4-di(4-methylphenyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   2-methyl-(3,4-di(4-methylphenyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   2-methyl-(3,4-di(4-methylphenyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   ((2,3-diphenyl)-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(t-butylamido)silane    titanium dichloride,-   ((2,3-diphenyl)-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(t-butylamido)silane    titanium dimethyl,-   ((2,3-diphenyl)-4-(N,N-dimethylainino)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   (2,3,4-triphenyl-5-metliylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (2,3,4-triphenyl-5-methylcyclopentadien-1-yl)dimetliyl(t-butylamido)silanetitaniium    dimethyl,-   (2,3,4-triphenyl-5-methylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   (3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   (2,3-diphenyl-4-(n-butyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (2,3-diphenyl-4-(n-butyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (2,3-diphenyl-4-(n-butyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   (2,3,4,5-tetraphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (2,3,4,5-tetraphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl, and-   (2,3,4,5-tetraphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene.

Additional examples of suitable metal complexes for use as catalyst (A)herein are polycyclic complexes corresponding to the formula:

where M is titanium in the +2, +3 or +4 formal oxidation state;

R⁷ independently each occurrence is hydride, hydrocarbyl, silyl, germyl,halide, hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino,di(hydrocarbyl)amino, hydrocarbyleneamino, di(hydrocarbyl)phosphino,hydrocarbylene-phosphino, hydrocarbylsulfido, halo-substitutedhydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, silyl-substitutedhydrocarbyl, hydrocarbylsiloxy-substituted hydrocarbyl,hydrocarbylsilylamino-substituted hyydrocarbyl,di(hydrocarbyl)amino-substituted hydrocarbyl,hydrocarbyleneamino-substituted hydrocarbyl,di(hydrocarbyl)phosphino-substituted hydrocarbyl,hydrocarbylene-phosphino-substituted hydrocarbyl, orhydrocarbylsulfido-substituted hydrocarbyl, said R⁷ group having up to40 atoms not counting hydrogen, and optionally two or more of theforegoing groups may together form a divalent derivative;

R⁸ is a divalent hydrocarbylene- or substituted hydrocarbylene groupforming a fused system with the remainder of the metal complex, said R⁸containing from 1 to 30 atoms not counting hydrogen;

X^(a) is a divalent moiety, or a moiety comprising one σ-bond and aneutral two electron pair able to form a coordinate-covalent bond to M,said X^(a) comprising boron, or a member of Group 14 of the PeriodicTable of the Elements, and also comprising nitrogen, phosphorus, sulfuror oxygen;

X is a monovalent anionic ligand group having up to 60 atoms exclusiveof the class of ligands that are cyclic, delocalized, π-bound ligandgroups and optionally two X groups together form a divalent ligandgroup;

Z independently each occurrence is a neutral ligating compound having upto 20 atoms;

x is 0, 1 or 2; and

z is zero or 1.

Preferred examples of such complexes are 3-phenyl-substituteds-indecenyl complexes corresponding to the formula:

2,3-dimethyl-substituted s-indecenyl complexes corresponding to theformulas:

or 2-methyl-substituted s-indecenyl complexes corresponding to theformula:

Additional examples of metal complexes that are usefully employed ascatalyst (A) according to the present invention include those of theformula:

Specific metal complexes include:

-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (II) 1,4-dipheniyl-1,3-butadiene,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethyletlhyl)dimetlhylsilanamide    titanium (II) 1,3-pentadiene,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (III) 2-(N,N-dimethylamino)benzyl,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (IV) dichloride,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethyletliyl)dimetliylsilanamide    titanium (IV) dimethyl,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimetllylethyl)dimetliylsilanamide    titanium (IV) dibenzyl,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (II) 1,4-diphenyl-1,3-butadiene,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (II) 1,3-pentadiene,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (III) 2-(N,N-dimethylamino)benzyl,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (IV) dichloride,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (IV) dimethyl,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (IV) dibenzyl,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimetliylsilanamide    titanium (II) 1,4-diphenyl-1,3-butadiene,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (II) 1,3-pentadiene,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (III) 2-(N,N-dimethylamino)benzyl,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimetllylsilanamide    titanium (IV) dichloride,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (IV) dimethyl,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (IV) dibenzyl,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimetliylsilanamide    titanium (II) 1,4-diphenyl-1,3-butadiene,-   (8-difluorometliylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (II) 1,3-pentadiene,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (III) 2-(N,N-dimethylamino)benzyl,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (IV) dichloride,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (IV) dimethyl,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titaniuin (IV) dibenzyl, and mixtures thereof, especially mixtures    of positional isomers.

Further illustrative examples of metal complexes for use according tothe present invention correspond to the formula:

where M is titanium in the +2, +3 or +4 formal oxidation state;

T is —NR⁹— or —O—;

R⁹ is hydrocarbyl, silyl, germyl, dihydrocarbylboryl, or halohydrocarbylor up to 10 atoms not counting hydrogen;

R¹⁰ independently each occurrence is hydrogen, hydrocarbyl,trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, germyl, halide,hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino,di(hydrocarbyl)amino, hydrocarbyleneamino, di(hydrocarbyl)phosphino,hydrocarbylene-phosphino, hydrocarbylsulfido, halo-substitutedhydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, silyl-substitutedhydrocarbyl, hydrocarbylsiloxy-substituted hydrocarbyl,hydrocarbylsilylamino-substituted hydrocarbyl,di(hydrocarbyl)amino-substituted hydrocarbyl,hydrocarbyleneamino-substituted hydrocarbyl,di(hydrocarbyl)phosphino-substituted hydrocarbyl,hydrocarbylenephosphino-substituted hydrocarbyl, orhydrocarbylsulfido-substituted hydrocarbyl, said R¹⁰ group having up to40 atoms not counting hydrogen atoms, and optionally two or more of theforegoing adjacent R¹⁰ groups may together form a divalent derivativethereby forming a saturated or unsaturated fused ring;

X^(a) is a divalent moiety lacking in delocalized π-electrons, or such amoiety comprising one σ-bond and a neutral two electron pair able toform a coordinate-covalent bond to M, said X′ comprising boron, or amember of Group 14 of the Periodic Table of the Elements, and alsocomprising nitrogen, phosphorus, sulfur or oxygen;

X is a monovalent anionic ligand group having up to 60 atoms exclusiveof the class of ligands that are cyclic ligand groups bound to M throughdelocalized π-electrons or two X groups together are a divalent anionicligand group;

Z independently each occurrence is a neutral ligating compound having upto 20 atoms;

x is 0, 1, 2, or 3; and

z is 0 or 1.

Highly preferably T is ═N(CH₃), X is halo or hydrocarbyl, x is 2, X′ isdimethylsilane, z is 0, and R¹⁰ each occurrence is hydrogen, ahydrocarbyl, hydrocarbyloxy, dihydrocarbylamino, hydrocarbyleneamino,dihydrocarbylamino-substituted hydrocarbyl group, orhydrocarbyleneamino-substituted hydrocarbyl group of up to 20 atoms notcounting hydrogen, and optionally two R¹⁰ groups may be joined together.

Illustrative metal complexes of the foregoing formula that may beemployed in the practice of the present invention further include thefollowing compounds:

-   (t-butylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (II)    1,4-diphenyl-1,3-butadiene,-   (t-butylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (II)    1,3-pentadiene,-   (t-butylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (III)    2-(N,N-dimethylamino)benzyl,-   (t-butylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    dichloride,-   (t-butylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    dimethyl,-   (t-butylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    dibenzyl,-   (t-butylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    bis(trimethylsilyl),-   (cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (II)    1,4-diphenyl-1,3-butadiene,-   (cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (II)    1,3-pentadiene,-   (cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (III)    2-(N,N-dimethylamino)benzyl,-   (cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    dichloride,-   (cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    dimethyl,-   (cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    dibenzyl,-   (cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    bis(trimethylsilyl),-   (t-butylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (II)    1,4-diphenyl-1,3-butadiene,-   (t-butylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (II)    1,3-pentadiene,-   (t-butylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (III)    2-(N,N-dimethylamino)benzyl,-   (t-butylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    dichloride,-   (t-butylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    dimethyl,-   (t-butylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    dibenzyl,-   (t-butylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    bis(trimetliylsilyl),-   (cyclohexylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (II)    1,4-diphenyl-1,3-butadiene,-   (cyclohexylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (II)    1,3-pentadiene,-   (cyclohexylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (III)    2-(N,N-dimethylamino)benzyl,-   (cyclohexylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-metlylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    dichloride,-   (cyclohexylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    dimethyl,-   (cyclohexylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    dibenzyl; and-   (cyclohexylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    bis(trimethylsilyl).

Illustrative Group 4 metal complexes that may be employed in thepractice of the present invention further include:

-   (tert-butylamido)1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalenyl)dimethylsilanetitaniumdimethyl,-   (tert-butylamido)(1,1,2,3-tetrametliyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalenyl)dimethylsilanetitaniumdimethyl,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)    dimethylsilanetitanium dibenzyl,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium    dimethyl,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyltitanium    dimethyl,-   (tert-butylamido)(tetramethyl-η⁵-indenyl)dimethylsilanetitanium    dimethyl,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilane    titanium (III) 2-(dimethylamino)benzyl;-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilaletitanium (III)    allyl,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium (III)    2,4-dimethylpentadienyl,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium (II)    1,4-diphenyl-1,3-butadiene,-   (tert-butylamido)(tetramethyl-η⁵-cyclopeiitadieny3)dimethylsilanetitanium (II)    1,3-pentadiene,-   (tert-butylamido)(2-metliylindeiiyl)dimethylsilanetitanium (II)    1,4-diphenyl-1,3-butadiene,-   (tert-butylamido)(2-metlhylindenyl)dimethylsilanetitanium (II)    2,4-hexadiene,-   (tert-butylainido)(2-metliylindenyl)dimethylsilanetitanium (IV)    2,3-dimethyl-1,3-butadiene,-   (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV)    isoprene,-   (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV)    1,3-butadiene,-   (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)    2,3-dimethyl-1,3-butadiene,-   (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)    isoprene-   (tert-butylamnido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)    dimethyl-   (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)    dibenzyl-   (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)    1,3-butadiene,-   (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (II)    1,3-pentadiene,-   (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (II)    1,4-diphenyl-1,3-butadiene,-   (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (II)    1,3-pentadiene,-   (tert-butylamido)(2-metlhylindenyl)dimethylsilanetitanium (IV)    dimethyl,-   (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV)    dibenzyl,-   (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium (II)    1,4-diphenyl-1,3-butadiene,-   (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium (II)    1,3-pentadiene,-   (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium (II)    2,4-hexadiene,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium (IV)    1,3-butadiene,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl    )dimetlylsilanetitaiium (IV) 2,3-dimethyl-1,3-butadiene,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium (IV)    isoprene,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimetliyl-silanetitanium (II)    1,4-dibenzyl-1,3-butadiene,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium (II)    2,4-hexadiene,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimetliyl-silanetitanium (II)    3-methyl-1,3-pentadiene,-   (tert-butylamido)(2,4-dimethylpentadien-3-yl)dimethylsilanetitaniumdimethyl,-   (tert-butylamido)(6,6-dimethylcyclohexadienyl)dimethylsilanetitaniumdimethyl,-   (tert-butylamido)(1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanetitaniumdimethyl,-   (tert-butylamido)(1,1,2,3-tetramethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanetitaniumdimethyl-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl    methylphenylsilanetitanium (IV) dimethyl,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl    methylphenylsilanetitanium (II) 1,4-diphenyl-1,3-butadiene,-   1-(tert-butylamido)-2-(tetramethyl-η⁵-cyclopentadienyl)ethanediyltitanium (IV)    dimethyl, and-   1-(tert-butylamido)-2-(tetramethyl-η⁵-cyclopentadienyl)ethanediyl-titanium (II)    1,4-diphenyl-1,3-butadiene.

Other delocalized, π-bonded complexes, especially those containing otherGroup 4 metals, will, of course, be apparent to those skilled in theart, and are disclosed among other places in: WO 03/78480, WO 03/78483,WO 02/92610, WO 02/02577, US 2003/0004286 and U.S. Pat. Nos. 6,515,155,6,555,634, 6,150,297, 6,034,022, 6,268,444, 6,015,868, 5,866,704, and5,470,993.

Additional examples of metal complexes that are usefully employed ascatalyst (A) are complexes of polyvalent Lewis bases, such as compoundscorresponding to the formula:

wherein T^(b) is a bridging group, preferably containing 2 or more atomsother than hydrogen,

X^(b) and y^(b) are each independently selected from the groupconsisting of nitrogen, sulfur, oxygen and phosphorus; more preferablyboth X^(b) and Y^(b) are nitrogen, R^(b) and R^(b)′ independently eachoccurrence are hydrogen or C₁₋₅₀ hydrocarbyl groups optionallycontaining one or more heteroatoms or inertly substituted derivativethereof. Non-limiting examples of suitable R^(b) and R^(b)′ groupsinclude alkyl, alkenyl, aryl, aralkyl, (poly)alkylaryl and cycloalkylgroups, as well as nitrogen, phosphorus, oxygen and halogen substitutedderivatives thereof. Specific examples of suitable Rb and Rb′ groupsinclude methyl, ethyl, isopropyl, octyl, phenyl, 2,6-dimethylphenyl,2,6-di(isopropyl)phenyl, 2,4,6-trimethylphenyl, pentafluorophenyl,3,5-trifluoromethylphenyl, and benzyl;

g is 0 or 1;

M^(b) is a metallic element selected from Groups 3 to 15, or theLanthanide series of the Periodic Table of the Elements. Preferably,M^(b) is a Group 3-13 metal, more preferably M^(b) is a Group 4-10metal;

L^(b) is a monovalent, divalent, or trivalent anionic ligand containingfrom 1 to 50 atoms, not counting hydrogen. Examples of suitable L^(b)groups include halide; hydride; hydrocarbyl, hydrocarbyloxy;di(hydrocarbyl)amido, hydrocarbyleneamido, di(hydrocarbyl)phosphido;

hydrocarbylsulfido; hydrocarbyloxy, tri(hydrocarbylsilyl)alkyl; andcarboxylates. More preferred L^(b) groups are C₁₋₂₀ alkyl, C₇₋₂₀aralkyl, and chloride;

h is an integer from 1 to 6, preferably from 1 to 4, more preferablyfrom 1 to 3, and j is 1 or 2, with the value h×j selected to providecharge balance;

Z^(b) is a neutral ligand group coordinated to M^(b), and containing upto 50 atoms not counting hydrogen Preferred Z^(b) groups includealiphatic and aromatic amines, phosphines, and ethers, alkenes,alkadienes, and inertly substituted derivatives thereof. Suitable inertsubstituents include halogen, alkoxy, aryloxy, alkoxycarbonyl,aryloxycarbonyl, di(hydrocarbyl)amine, tri(hydrocarbyl)silyl, andnitrile groups. Preferred Z^(b) groups include triphenylphosphine,tetrahydrofuran, pyridine, and 1,4-diphenylbutadiene;

f is an integer from 1 to 3;

two or three of T^(b), R^(b) and R^(b)′ may be joined together to form asingle or multiple ring structure;

h is an integer from 1 to 6, preferably from 1 to 4, more preferablyfrom 1 to 3;

indicates any form of electronic interaction, especially coordinate orcovalent bonds, including multiple bonds, arrows signify coordinatebonds, and dotted lines indicate optional double bonds.

In one embodiment, it is preferred that R^(b) have relatively low sterichindrance with respect to X^(b). In this embodiment, most preferredR^(b) groups are straight chain alkyl groups, straight chain alkenylgroups, branched chain alkyl groups wherein the closest branching pointis at least 3 atoms removed from X^(b), and halo, dihydrocarbylamino,alkoxy or trihydrocarbylsilyl substituted derivatives thereof. Highlypreferred R^(b) groups in this embodiment are C₁₋₈ straight chain alkylgroups.

At the same time, in this embodiment R^(b)′ preferably has relativelyhigh steric hindrance with respect to Y^(b). Non-limiting examples ofsuitable R^(b)′ groups for this embodiment include alkyl or alkenylgroups containing one or more secondary or tertiary carbon centers,cycloalkyl, aryl, alkaryl, aliphatic or aromatic heterocyclic groups,organic or inorganic oligomeric, polymeric or cyclic groups, and halo,dihydrocarbylamino, alkoxy or trihydrocarbylsilyl substitutedderivatives thereof. Preferred R^(b)′ groups in this embodiment containfrom 3 to 40, more preferably from 3 to 30, and most preferably from 4to 20 atoms not counting hydrogen and are branched or cyclic.

Examples of preferred T^(b) groups are structures corresponding to thefollowing formulas:

Each R^(d) is C₁₋₁₀ hydrocarbyl group, preferably methyl, ethyl,n-propyl, i-propyl, t-butyl, phenyl, 2,6-dimethylphenyl, benzyl, ortolyl. Each R^(e) is C₁₋₁₀ hydrocarbyl, preferably methyl, ethyl,-n-propyl, i-propyl, t-butyl, phenyl, 2,6-dimethylphenyl, benzyl, ortolyl. In addition, two or more R^(d) or R^(e) groups, or mixtures of Rdand Re groups may together form a polyvalent derivative of a hydrocarbylgroup, such as, 1,4-butylene, 1,5-pentylene, or a multicyclic, fusedring, polyvalent hydrocarbyl- or heterolhydrocarbyl-group, such asnaphthalene-1,8-diyl.

Preferred examples of the foregoing polyvalent Lewis base complexesinclude:

wherein R^(d′) each occurrence is independently selected from the groupconsisting of hydrogen and C₁₋₅₀ hydrocarbyl groups optionallycontaining one or more heteroatoms, or inertly substituted derivativethereof, or further optionally, two adjacent R^(d′) groups may togetherform a divalent bridging group;

d′ is 4;

M^(b′) is a Group 4 metal, preferably titanium or hafnium, or a Group 10metal, preferably Ni or Pd;

L^(b′) is a monovalent ligand of up to 50 atoms not counting hydrogen,preferably halide or hydrocarbyl, or two L^(b′) groups together are adivalent or neutral ligand group, preferably a C₂₋₅₀ hydrocarbylene,hydrocarbadiyl or diene group.

The polyvalent Lewis base complexes for use in the present inventionespecially include Group 4 metal derivatives, especially hafniumderivatives of hydrocarbylamine substituted heteroaryl compoundscorresponding to the formula:

wherein:

R¹¹ is selected from alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl,aryl, and inertly substituted derivatives thereof containing from 1 to30 atoms not counting hydrogen or a divalent derivative thereof;

T¹ is a divalent bridging group of from 1 to 41 atoms other thanhydrogen, preferably 1 to 20 atoms atoms other than hydrogen, and mostpreferably a mono- or di-C₁₋₂₀ hydrocarbyl substituted methylene orsilane group; and

R¹² is a C₅₋₂₀ heteroaryl group containing Lewis base functionality,especially a pyridin-2-yl- or substituted pyridin-2-yl group or adivalent derivative thereof;

M¹ is a Group 4 metal, preferably hafnium;

X¹ is an anionic, neutral or dianionic ligand group;

x′ is a number from 0 to 5 indicating the number of such X¹ groups; and

bonds, optional bonds and electron donative interactions are representedby lines, dotted lines and arrows respectively.

Preferred complexes are those wherein ligand formation results fromhydrogen elimination from the amine group and optionally from the lossof one or more additional groups, especially from R¹². In addition,electron donation from the Lewis base functionality, preferably anelectron pair, provides additional stability to the metal center.Preferred metal complexes correspond to the formula:

M¹, X¹, x′, R¹¹ and T¹ are as previously defined, R¹³, R¹⁴, R¹⁵ and R¹⁶are hydrogen, halo, or an allyl, cycloalkyl, heteroalkyl,heterocycloalkyl, aryl, or silyl group of up to 20 atoms not countinghydrogen, or adjacent R¹³, R¹⁴, R¹⁵ or R¹⁶ groups may be joined togetherthereby forming fused ring derivatives, and

bonds, optional bonds and electron pair donative interactions arerepresented by lines, dotted lines and arrows respectively.

More preferred examples of the foregoing metal complexes correspond tothe formula:

M¹, X¹, and x′ are as previously defined,

R¹³, R¹⁴, R¹⁵ and R¹⁶ are as previously defined, preferably R¹³, R¹⁴,and R¹⁵ are hydrogen, or C₁₋₄ alkyl, and R¹⁶ is C₆₋₂₀ aryl, mostpreferably naphthalenyl;

R^(a) independently each occurrence is C₁₋₄ alkyl, and a is 1-5, mostpreferably R^(a) in two ortho-positions to the nitrogen is isopropyl ort-butyl;

R¹⁷ and R¹⁸ independently each occurrence are hydrogen, halogen, or aC₁₋₂₀ alkyl or aryl group, most preferably one of R¹⁷ and R¹⁸ ishydrogen and the other is a C₆₋₂₀ aryl group, especially 2-isopropyl,phenyl or a fused polycyclic aryl group, most preferably an anthracenylgroup, and

bonds, optional bonds and electron pair donative interactions arerepresented by lines, dotted lines and arrows respectively.

Highly preferred metal complexes for use herein as catalyst (A)correspond to the formula:

wherein X¹ each occurrence is halide, N,N-dimethylamido, or C₁₋₄ alkyl,and preferably each occurrence X¹ is methyl;

R^(f) independently each occurrence is hydrogen, halogen, C₁₋₂₀ alkyl,or C₆₋₂₀ aryl, or two adjacent R^(f) groups are joined together therebyforming a ring, and f is 1-5; and

R^(c) independently each occurrence is hydrogen, halogen, C₁₋₂₀ alkyl,or C₆₋₂₀ aryl, or two adjacent R^(c) groups are joined together therebyforming a ring, and c is 1-5.

Most highly preferred examples of metal complexes for use as catalyst(A) according to the present invention are complexes of the followingformulas:

wherein R^(x) is C₁₋₄ alkyl or cycloalkyl, preferably methyl, isopropyl,t-butyl or cyclohexyl; and

X¹ each occurrence is halide, N,N-dimethylamido, or C₁₋₄ alkyl,preferably methyl.

Examples of metal complexes usefully employed as catalyst (A) accordingto the present invention include:

-   [N-(2,6-di(1-methylethyl)phenyl)amido)(o-tolyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    dimethyl;-   [N-(2,6-di(1-methyletlyl)phenyl)amido)(o-tolyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    di(N,N-dimethylamido);-   [N-(2,6-di(1-methylethyl)phenyl)amido)(o-tolyl)((α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    dichloride;-   [N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    dimethyl;-   [N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)((α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    di(N,N-dimethylamido);-   [N-(2,6-di(1-metlylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphtlalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    dichloride;-   [N-(2,6-di(1-methylethyl)phenyl)amido)(phenanthren-5-yl)((α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    dimethyl;-   [N-(2,6-di(1-methylethyl)phenyl)amido)(phenanthren-5-yl)((α-naphtlalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    di(N,N-dimethylamido); and-   [N-(2,6-di(1-methylethyl)phenyl)amido)(phenanthren-5-yl)((α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    dichloride.

Under the reaction conditions used to prepare the metal complexes usedin the present invention, the hydrogen of the 2-position of the(x-naphthalene group substituted at the 6-position of the pyridin-2-ylgroup is subject to elimination, thereby uniquely forming metalcomplexes wherein the metal is covalently bonded to both the resultingamide group and to the 2-position of the α-naphthalenyl group, as wellas stabilized by coordination to the pyridinyl nitrogen atom through theelectron pair of the nitrogen atom.

Group 4-10 derivatives corresponding to the formula:

wherein

-   -   M² is a metal of Groups 4-10 of the Periodic Table of the        elements, preferably Group 4 metals, Ni(II) or Pd(II), most        preferably zirconium;    -   T² is a nitrogen, oxygen or phosphorus containing group;    -   X² is halo, hydrocarbyl, or hydrocarbyloxy;    -   t is one or two;    -   x″ is a number selected to provide charge balance;    -   and T² and N are linked by a bridging ligand.

Such catalysts have been previously disclosed in J. Am. Chem. Soc., 118,267-268 (1996), J. Am. Chem. Soc., 117, 6414-6415 (1995), andOrganometallics, 16, 1514-1516, (1997), among other disclosures.

Examples of the foregoing metal complexes include aromatic diimine oraromatic dioxyimine complexes of Group 4 metals, especially zirconium,corresponding to the formula:

wherein,

M², X² and T² are as previously defined;

R^(d) independently each occurrence is hydrogen, halogen, or R^(e); and

R^(e) independently each occurrence is C₁₋₂₀ hydrocarbyl or aheteroatom-, especially a F, N, S or P-substituted derivative thereof,more preferably C₁₋₁₀ hydrocarbyl or a F or N substituted derivativethereof, most preferably alkyl, dialkylaminoalkyl, pyrrolyl,piperidenyl, perfluorophenyl, cycloalkyl, (poly)alkylaryl, or aralkyl.

Most preferred examples of the foregoing metal complexes are aromaticdioxyimine complexes of zirconium, corresponding to the formula:

wherein;

X² is as previously defined, preferably C₁₋₁₀ hydrocarbyl, mostpreferably methyl or benzyl; and

R^(e)′ is methyl, isopropyl, t-butyl, cyclopentyl, cyclohexyl,2-metlhylcyclohexyl, 2,4-dimethylcyclohexyl, 2-pyrrolyl,N-methyl-2-pyrrolyl, 2-piperidenyl, N-methyl-2-piperidenyl, benzyl,o-tolyl, 2,6-dimethylphenyl, perfluorophenyl, 2,6-di(isopropyl)phenyl,or 2,4,6-trimethylphenyl.

The foregoing complexes also include certain phosphininine complexesdisclosed in EP-A-890581. These complexes correspond to the formula:[(R^(f))₃—P═N]_(f)M(K²)(R^(f))_(3-f), wherein:

R^(f) is a monovalent ligand or two R^(f) groups together are a divalentligand, preferably R^(f) is hydrogen or C₁₋₄ alkyl;

M is a Group 4 metal,

K² is a group containing delocalized π-electrons through which K² isbound to M, said K² group containing up to 50 atoms not countinghydrogen atoms, and

f is 1 or 2.

Additional suitable metal complexes of polyvalent Lewis bases for useherein include compounds corresponding to the formula:

R²⁰ is an aromatic or inertly substituted aromatic group containing from5 to 20 atoms not counting hydrogen, or a polyvalent derivative thereof;

T³ is a hydrocarbylene or silane group having from 1 to 20 atoms notcounting hydrogen, or an inertly substituted derivative thereof;

M³ is a Group 4 metal, preferably zirconium or hafnium;

G is an anionic, neutral or dianionic ligand group; preferably a halide,hydrocarbyl or dihydrocarbylamide group having up to 20 atoms notcounting hydrogen;

g is a number from 1 to 5 indicating the number of such G groups; and

bonds and electron donative interactions are represented by lines andarrows respectively.

Preferably, such complexes correspond to the formula:

T³ is a divalent bridging group of from 2 to 20 atoms not countinghydrogen, preferably a substituted or unsubstituted, C₃₋₆ alkylenegroup; and

Ar² independently each occurrence is an arylene or an alkyl- oraryl-substituted arylene group of from 6 to 20 atoms not countinghydrogen;

M³ is a Group 4 metal, preferably hafnium or zirconium;

G independently each occurrence is an anionic, neutral or dianionicligand group;

g is a number from 1 to 5 indicating the number of such X groups; and

electron donative interactions are represented by arrows.Preferred examples of metal complexes of foregoing formula include thefollowing compounds:

where M³ is Hf or Zr;

Ar⁴ is C₆₋₂₀ aryl or inertly substituted derivatives thereof, especially3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl,dibenzo-1H-pyrrole-1-yl, or anthracen-5-yl, and

T⁴ independently each occurrence comprises a C₃₋₆ alkylene group, a C₃₋₆cycloalkylene group, or an inertly substituted derivative thereof;

R²¹ independently each occurrence is hydrogen, halo, hydrocarbyl,trihydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl of up to 50 atomsnot counting hydrogen; and

G, independently each occurrence is halo or a hydrocarbyl ortrihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2G groups together are a divalent derivative of the foregoing hydrocarbylor trihydrocarbylsilyl groups.

Especially preferred are compounds of the formula:

wherein Ar⁴ is 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl,dibenzo-1H-pyrrole-1-yl, or anthracen-5-yl,

R²¹ is hydrogen, halo, or C₁₋₄ alkyl, especially methyl

T⁴ is propan-1,3-diyl or butan-1,4-diyl, and

G is chloro, methyl or benzyl.

Additional metal complexes are those of the foregoing formula:

The foregoing polyvalent Lewis base complexes are conveniently preparedby standard metallation and ligand exchange procedures involving asource of the Group 4 metal and the neutral polyfunctional ligandsource. In addition, the complexes may also be prepared by means of anamide elimination and hydrocarbylation process starting from thecorresponding Group 4 metal tetraamide and a hydrocarbylating agent,such as trimethylaluminum. Other techniques may be used as well. Thesecomplexes are known from the disclosures of, among others, U.S. Pat.Nos. 6,320,005, 6,103,657, WO 02/38628, WO 03/40195, and U.S. Ser. No.04/022,0050.

Suitable metal compounds for use as catalyst (B) include the foregoingmetal compounds mentioned with respect to catalyst (A) as well as othermetal compounds, with the proviso, that they result in formation of atleast some hyperbranch- or long chain branch-formation.

Catalysts having high comonomer incorporation properties are also knownto reincorporate in situ prepared long chain olefins resultingincidentally during the polymerization through , β-hydride eliminationand chain termination of growing polymer, or other process. Theconcentration of such long chain olefins is particularly enhanced by useof continuous solution polymerization conditions at high conversions,especially ethylene conversions of 95 percent or greater, morepreferably at ethylene conversions of 97 percent or greater. Under suchconditions a small but detectable quantity of olefin terminated polymermay be reincorporated into a growing polymer chain, provided that vinylterminated polymer chains are present, normally as a result of β-hydrideelimination, resulting in the formation of long chain branches, that is,branches of a carbon length greater than result from the monomer itself.Long chain branching of olefin polymers is further described in U.S.Pat. Nos. 5,272,236, 5,278,272, and 5,665,800.

Alternatively, and more preferably, branching, includinghyper-branching, is induced in a particular segment of the presentmulti-block copolymers by the use of specific catalysts known to resultin “chain-walking” in the resulting polymer. Preferred catalysts arethose based on the higher transition metal complexes, especially nickeland palladium diimines.

In one embodiment of the invention, the presence of such branching (longchain branching, 1,3-addition, or hyper-branching) in the polymers ofthe invention can be confined to only the blocks or segments resultingfrom activity of catalyst B. Accordingly, in one embodiment of theinvention a multi-block copolymer containing blocks or segmentsdiffering in the presence of such branching in combination with othersegments or blocks substantially lacking such branching (especially highdensity or highly crystalline polymer blocks), can be produced from asingle monomer containing reaction mixture, that is, without theaddition of a deliberately added comonomer. Highly preferably, in aspecific embodiment of the invention, a multi-block copolymer comprisingalternating unbranched, ethylene homopolymer segments and branchedpolyethylene segments, especially ethylene/propylene copolymer segments,may be prepared from an initial reaction mixture consisting essentiallyof ethylene as the addition polymerizable monomer. The presence of suchbranching in the multi-block copolymers of the invention can be detectedby certain physical properties of the resulting copolymers, such asreduced surface imperfections during melt extrusion (reduced meltfracture), reduced melting point, Tg, for the amorphous segmentscompared to a non-branched polymer segment, and/or the presence of1,3-addition sequences or hyper-branching as detected by NMR techniques.The quantity of the foregoing types of branching present in the polymersof the invention (as a portion of the blocks or segments containing thesame), is normally in the range from 0.01 to 10 branches per 1,000carbons.

In addition to the previously identified metal complexes for use ascatalyst (A), the following metal compounds or inertly coordinatedderivatives thereof are especially suited for use as catalyst (B):racemic ethylene bisindenyl complexes of Group 4 metals, especially Zr,and inertly substituted derivatives thereof, such as 1-, or2-t-butyldimethylsiloxy-substituted ethylene bis(indenyl)zirconiumcomplexes, as disclosed in Macromolecules 33, 9200-9204 (2000),ethylenebis(4,5,6,7-tetrahydro-1-indenyl) zirconium-complexes, racemicethylene bis(indenyl)zirconium complexes, and metal complexes of theformula:

where M′ is a metal of Groups 4-13, preferably Groups 8-10, mostpreferably Ni or Pd;

R^(A), R^(B) and R^(C) are univalent or neutral substituents, which alsomay be joined together to form one or more divalent substituents, and

c is a number chosen to balance the charge of the metal complex.

Preferred examples of the foregoing metal complexes for use as catalysts(B) are compounds corresponding to the formula:

wherein M′ is Pd or Ni.

Cocatalysts

Each of the metal complex catalysts (A) and (B) (also interchangeablyreferred to herein as procatalysts) may be activated to form the activecatalyst composition by combination with a cocatalyst, preferably acation forming cocatalyst, a strong Lewis acid, or a combinationthereof. In a preferred embodiment, the shuttling agent is employed bothfor purposes of chain shuttling and as the cocatalyst component of thecatalyst composition.

The metal complexes desirably are rendered catalytically active bycombination with a cation forming cocatalyst, such as those previouslyknown in the art for use with Group 4 metal olefin polymerizationcomplexes. Suitable cation forming cocatalysts for use herein includeneutral Lewis acids, such as C₁₋₃₀ hydrocarbyl substituted Group 13compounds, especially tri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boroncompounds and halogenated (including perhalogenated) derivativesthereof, having from 1 to 10 carbons in each hydrocarbyl or halogenatedhydrocarbyl group, more especially perfluorinated tri(aryl)boroncompounds, and most especially tris(pentafluoro-phenyl)borane;nonpolymeric, compatible, noncoordinating, ion forming compounds(including the use of such compounds under oxidizing conditions),especially the use of ammonium-, phosphonium-, oxonium-, carbonium-,silylium- or sulfonium-salts of compatible, noncoordinating anions, orferrocenium-, lead- or silver salts of compatible, noncoordinatinganions; and combinations of the foregoing cation forming cocatalysts andtechniques. The foregoing activating cocatalysts and activatingtechniques have been previously taught with respect to different metalcomplexes for olefin polymerizations in the following references:EP-A-277,003, U.S. Pat. No. 5,153,157, U.S. Pat. No. 5,064,802, U.S.Pat. No. 5,321,106, U.S. Pat. No. 5,721,185, U.S. Pat. No. 5,350,723,U.S. Pat. No. 5,425,872, U.S. Pat. No. 5,625,087, U.S. Pat. No.5,883,204, U.S. Pat. No. 5,919,983, U.S. Pat. No. 5,783,512, WO99/15534, and WO99/42467.

Combinations of neutral Lewis acids, especially the combination of atriallyl aluminum compound having from 1 to 4 carbons in each alkylgroup and a halogenated tri(hydrocarbyl)boron compound having from 1 to20 carbons in each hydrocarbyl group, especiallytris(pentafluorophenyl)borane, further combinations of such neutralLewis acid mixtures with a polymeric or oligomeric alumoxane, andcombinations of a single neutral Lewis acid, especiallytris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxanemay be used as activating cocatalysts. Preferred molar ratios of metalcomplex:tris(pentafluorophenyl-borane:alumoxane are from 1:1:1 to1:5:20, more preferably from 1:1:1.5 to 1:5:10.

Suitable ion forming compounds useful as cocatalysts in one embodimentof the present invention comprise a cation which is a Bronsted acidcapable of donating a proton, and a compatible, noncoordinating anion,A⁻. As used herein, the term “noncoordinating” means an anion orsubstance which either does not coordinate to the Group 4 metalcontaining precursor complex and the catalytic derivative derived therefrom, or which is only weakly coordinated to such complexes therebyremaining sufficiently labile to be displaced by a neutral Lewis base. Anoncoordinating anion specifically refers to an anion which whenfunctioning as a charge balancing anion in a cationic metal complex doesnot transfer an anionic substituent or fragment thereof to said cationthereby forming neutral complexes. “Compatible anions” are anions whichare not degraded to neutrality when the initially formed complexdecomposes and are noninterfering with desired subsequent polymerizationor other uses of the complex.

Preferred anions are those containing a single coordination complexcomprising a charge-bearing metal or metalloid core which anion iscapable of balancing the charge of the active catalyst species (themetal cation) which may be formed when the two components are combined.Also, said anion should be sufficiently labile to be displaced byolefinic, diolefinic and acetylenically unsaturated compounds or otherneutral Lewis bases such as ethers or nitriles. Suitable metals include,but are not limited to, aluminum, gold and platinum. Suitable metalloidsinclude, but are not limited to, boron, phosphorus, and silicon.Compounds containing anions which comprise coordination complexescontaining a single metal or metalloid atom are, of course, well knownand many, particularly such compounds containing a single boron atom inthe anion portion, are available commercially.

Preferably such cocatalysts may be represented by the following generalformula:(L*-H)_(g) ⁺(A)^(g−)wherein:

L* is a neutral Lewis base;

(L*-H)⁺ is a conjugate Bronsted acid of L*;

A^(g−) is a noncoordinating, compatible anion having a charge of g−, andg is an integer from 1 to 3.

More preferably A^(g−) corresponds to the formula: [M′Q₄]⁻;

wherein:

M′ is boron or aluminum in the +3 formal oxidation state; and

Q independently each occurrence is selected from hydride, dialkylamido,halide, hydrocarbyl, hydrocarbyloxide, halosubstituted-hydrocarbyl,halosubstituted hydrocarbyloxy, and halo-substituted silylhydrocarbylradicals (including perhalogenated hydrocarbyl-perhalogenatedhydrocarbyloxy- and perhalogenated silylhydrocarbyl radicals), said Qhaving up to 20 carbons with the proviso that in not more than oneoccurrence is Q halide. Examples of suitable hydrocarbyloxide Q groupsare disclosed in U.S. Pat. No. 5,296,433.

In a more preferred embodiment, d is one, that is, the counter ion has asingle negative charge and is A⁻. Activating cocatalysts comprisingboron which are particularly useful in the preparation of catalysts ofthis invention may be represented by the following general formula:(L*-H)⁺(BQ₄)⁻;wherein:

L* is as previously defined;

B is boron in a formal oxidation state of 3; and

Q is a hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl-,fluorinated hydrocarbyloxy-, or fluorinated silylhydrocarbyl-group of upto 20 nonhydrogen atoms, with the proviso that in not more than oneoccasion is Q hydrocarbyl.

Preferred Lewis base salts are ammonium salts, more preferablytriallylammonium salts containing one or more C₁₂₋₄₀ alkyl groups. Mostpreferably, Q is each occurrence a fluorinated aryl group, especially, apentafluorophenyl group.

Illustrative, but not limiting, examples of boron compounds which may beused as an activating cocatalyst in the preparation of the improvedcatalysts of this invention are tri-substituted ammonium salts such as:

trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumn-butyltris(pentafluorophenyl)borate, N,N-dimethylaniliniumbenzyltris(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(4-(t-butyldimethylsilyl)-2,3,5,6-tetrafluorophenyl)borate,N,N-dimethylaniliniumtetrakis(4-(triisopropylsilyl)-2,3,5,6-tetrafluorophenyl)borate,N,N-dimethylanilinium pentafluorophenoxytris(pentafluorophenyl)borate,N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(pentafluorophenyl)borate,dimethyloctadecylammonium tetrakis(pentafluorophenyl)borate,methyldioctadecylammonium tetrakis(pentafluorophenyl)borate, dialkylammonium salts such as:

di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate,methyloctadecylarnmonium tetrakis(pentafluorophenyl)borate,methyloctadodecylammonium tetrakis(pentafluorophenyl)borate, anddioctadecylammonium tetrakis(pentafluorophenyl)borate; tri-substitutedphosphonium salts such as:

triphenylphosphonium tetrakis(pentafluorophenyl)borate,methyldioctadecylphosphonium tetrakis(pentafluorophenyl)borate, andtri(2,6-dimethylpheniyl)phosphonium tetrakis(pentafluorophenyl)borate;di-substituted oxonium salts such as:

diphenyloxonium tetrakis(pentafluorophenyl)borate, di(o-tolyl)oxoniumtetrakis(pentafluorophenyl)borate, and di(octadecyl)oxoniumtetrakis(pentafluorophenyl)borate; di-substituted sulfonium salts suchas:

di(o-tolyl)sulfonium tetrakis(pentafluorophenyl)borate, andmethylcotadecylsulfonium tetrakis(pentafluorophenyl)borate.

Preferred (L*-H)⁺ cations are methyldioctadecylammonium cations,dimethyloctadecylammonium cations, and ammonium cations derived frommixtures of trialkyl amines containing one or 2 C₁₄₋₁₈ alkyl groups.

Another suitable ion forming, activating cocatalyst comprises a salt ofa cationic oxidizing agent and a noncoordinating, compatible anionrepresented by the formula:(Oxh^(h+))_(g)(A^(g−))_(h),wherein:

Ox^(h+) is a cationic oxidizing agent having a charge of h+;

h is an integer from 1 to 3; and

A^(g−) and g are as previously defmed.

Examples of cationic oxidizing agents include: ferrocenium,hydrocarbyl-substituted ferrocenium, Ag⁺′ or Pb⁺². Preferred embodimentsof A^(g−) are those anions previously defined with respect to theBronsted acid containing activating cocatalysts, especiallytetrakis(pentafluorophenyl)borate.

Another suitable ion forming, activating cocatalyst comprises a compoundwhich is a salt of a carbenium ion and a noncoordinating, compatibleanion represented by the formula:[C]⁺ A⁻wherein:

[C]⁺ is a C₁₋₂₀ carbenium ion; and

A⁻ is a noncoordinating, compatible anion having a charge of −1. Apreferred carbenium ion is the trityl cation, that istriphenylmethylium.

A further suitable ion forming, activating cocatalyst comprises acompound which is a salt of a silylium ion and a noncoordinating,compatible anion represented by the formula:(Q¹ ₃Si)⁺A⁻wherein:

Q¹ is C₁₋₁₀ hydrocarbyl, and A⁻ is as previously defined.

Preferred silylium salt activating cocatalysts are trimethylsilyliumtetrakispentafluorophenylborate, triethylsilyliumtetrakispentafluorophenylborate and ether substituted adducts thereof.Silylium salts have been previously generically disclosed in J. ChemSoc. Chem. Comm., 1993, 383-384, as well as Lambert, J. B., et al.,Organometallics, 1994, 13, 2430-2443. The use of the above silyliumsalts as activating cocatalysts for addition polymerization catalysts isdisclosed in U.S. Pat. No. 5,625,087.

Certain complexes of alcohols, mercaptans, silanols, and oximes withtris(pentafluorophenyl)borane are also effective catalyst activators andmay be used according to the present invention. Such cocatalysts aredisclosed in U.S. Pat. No. 5,296,433.

Suitable activating cocatalysts for use herein also include polymeric oroligomeric alumoxanes, especially methylalumoxane (MAO), triisobutylaluminum modified metliylalumoxane (MMAO), or isobutylalumoxane; Lewisacid modified alumoxanes, especially perhalogenatedtri(hydrocarbyl)aluminum- or perhalogenated tri(hydrocarbyl)boronmodified alumoxanes, having from 1 to 10 carbons in each hydrocarbyl orhalogenated hydrocarbyl group, and most especiallytris(pentafluorophenyl)borane modified alumoxanes. Such cocatalysts arepreviously disclosed in U.S. Pat. Nos. 6,214,760, 6,160,146, 6,140,521,and 6,696,379.

A class of cocatalysts comprising non-coordinating anions genericallyreferred to as expanded anions, further disclosed in U.S. Pat. No.6,395,671, may be suitably employed to activate the metal complexes ofthe present invention for olefin polymerization. Generally, thesecocatalysts (illustrated by those having imidazolide, substitutedimidazolide, imidazolinide, substituted imidazolinide, benzimidazolide,or substituted benzimidazolide anions) may be depicted as follows:

wherein:

A^(*+) is a cation, especially a proton containing cation, andpreferably is a trihydrocarbyl ammonium cation containing one or twoC₁₀₋₄₀ alkyl groups, especially a methyldi (C₁₄₋₂₀ alkyl)ammoniumcation,

Q³, independently each occurrence, is hydrogen or a halo, hydrocarbyl,halocarbyl, halohydrocarbyl, silylhydrocarbyl, or silyl, (includingmono-, di- and tri(hydrocarbyl)silyl) group of up to 30 atoms notcounting hydrogen, preferably C₁₋₂₀ alkyl, and

Q² is tris(pentafluorophenyl)borane or tris(pentafluorophenyl)alumane).

Examples of these catalyst activators includetrihydrocarbylammonium-salts, especially, methyldi(C₁₄₋₂₀alkyl)ammonium-salts of:

bis(tris(pentafluorophenyl)borane)imidazolide,bis(tris(pentafluorophenyl)borane)-2-undecylimidazolide,bis(tris(pentafluorophei-yl)borane)-2-heptadecylimidazolide,bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolide,bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolide,bis(tris(pentafluorophenyl)borane)imidazolinide,bis(tris(pentafluorophenyl)borane)-2-undecylimidazolinide,bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolinide,bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolinide,bis(tris(peltafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolinide,bis(tris(pentafluorophenyl)borane)-5,6-dimethylbenzimidazolide,bis(tris(pentafluorophenyl)borane)-5,6-bis(undecyl)benzimidazolide,

bis(tris(pentafluorophenyl)alumarie)imidazolide,bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolide,bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolide,bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolide,bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolide,bis(tris(pentafluorophenyl)alumane)imidazolinide,bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolinide,bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolinide,bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolinide,bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolinide,bis(tris(pentafluorophenyl)alumane)-5,6-dimethylbenzimidazolide, andbis(tris(peitafluorophenyl)alumane)-5,6-bis(undecyl)benzimidazolide.

Other activators include those described in PCT publication WO 98/07515such as tris (2,2′,2″-nonafluorobiphenyl)fluoroaluminate. Combinationsof activators are also contemplated by the invention, for example,alumoxanes and ionizing activators in combinations, see for example,EP-A-0 573120, PCT publications WO 94/07928 and WO 95/14044 and U.S.Pat. Nos. 5,153,157 and 5,453,410. WO 98/09996 describes activatingcatalyst compounds with perchlorates, periodates and iodates, includingtheir hydrates. WO 99/18135 describes the use of organoboroaluminumactivators. WO 03/10171 discloses catalyst activators that are adductsof Bronsted acids with Lewis acids. Other activators or methods foractivating a catalyst compound are described in for example, U.S. Pat.Nos. 5,849,852, 5,859,653, 5,869,723, EP-A-615981, and PCT publicationWO 98/32775. All of the foregoing catalyst activators as well as anyother know activator for transition metal complex catalysts may beemployed alone or in combination according to the present invention,however, for best results alumoxane containing cocatalysts are avoided.

The molar ratio of catalyst/cocatalyst employed preferably ranges from1:10,000 to 100:1, more preferably from 1:5000 to 10:1, most preferablyfrom 1:1000 to 1:1. Alumoxane, when used by itself as an activatingcocatalyst, is employed in large quantity, generally at least 100 timesthe quantity of metal complex on a molar basis.Tris(pentafluorophenyl)borane, where used as an activating cocatalyst isemployed in a molar ratio to the metal complex of from 0.5:1 to 10:1,more preferably from 1:1 to 6:1 most preferably from 1:1 to 5:1. Theremaining activating cocatalysts are generally employed in approximatelyequimolar quantity with the metal complex.

The process of the invention employing catalyst A, catalyst B, one ormore cocatalysts, and chain shuttling agent C may be further elucidatedby reference to FIG. 1, where there are illustrated activated catalystsite A, 10, which under polymerization conditions forms a polymer chain,13, attached to the active catalyst site, 12. Similarly, active catalystsite B, 20, produces a differentiated polymer chain, 23, attached to theactive catalyst site, 22. A chain shuttling agent C1, attached to apolymer chain produced by active catalyst B, 14, exchanges its polymerchain, 23, for the polymer chain, 13, attached to catalyst site A.Additional chain growth under polymerization conditions causes formationof a multi-block copolymer, 18, attached to active catalyst site A.Similarly, chain shuttling agent C2, attached to a polymer chainproduced by active catalyst site A, 24, exchanges its polymer chain, 13,for the polymer chain, 23, attached to catalyst site B. Additional chaingrowth under polymerization conditions causes formation of a multi-blockcopolyiner, 28, attached to active catalyst site B. The growingmulti-block copolymers are repeatedly exchanged between active catalystA and active catalyst B by means of shuttling agent C resulting information of a block or segment of differing properties wheneverexchange to the opposite active catalyst site occurs. The growingpolymer chains may be recovered while attached to a chain shuttlingagent and functionalized if desired. Alternatively, the resultingpolymer may be recovered by scission from the active catalyst site orthe shuttling agent, through use of a proton source or other killingagent.

It is believed (without wishing to be bound by such belief), that thecomposition of the respective segments or blocks, and especially of theend segments of the polymer chains, may be influenced through selectionof process conditions or other process variables. In the polymers of theinvention, the nature of the end segments is determined by the relativerates of chain transfer or termination for the respective catalysts aswell as by the relative rates of chain shuttling. Possible chaintermination mechanisms include, but are not limited to, β-hydrogenelimination, β-hydrogen transfer to monomer, β-methyl elimination, andchain transfer to hydrogen or other chain-terminating reagent such as anorganosilane or chain functionalizing agent. Accordingly, when a lowconcentration of chain shuttling agent is used, the majority of polymerchain ends will be generated in the polymerization reactor by one of theforegoing chain termination mechanisms and the relative rates of chaintermination for catalyst (A) and (B) will determine the predominantchain terminating moiety. That is, the catalyst having the fastest rateof chain termination will produce relatively more chain end segments inthe finished polymer.

In contrast, when a high concentration of chain shuttling agent isemployed, the majority of the polymer chains within the reactor and uponexiting the polymerization zone are attached or bound to the chainshuttling agent. Under these reaction conditions, the relative rates ofchain transfer of the polymerization catalysts and the relative rate ofchain shuttling of the two catalysts primarily determines the identityof the chain terminating moiety. If catalyst (A) has a faster chaintransfer and/or chain shuttling rate than catalyst (B), then themajority of the chain end segments will be those produced by catalyst(A).

At intermediate concentrations of chain shuttling agent, all three ofthe aforementioned factors are instrumental in determining the identityof the final polymer block. The foregoing methodology may be expanded tothe analysis of multi-block polymers having more than two block typesand for controlling the average block lengths and block sequences forthese polymers. For example, using a mixture of catalysts 1, 2, and 3with a chain shuttling agent, for which each catalyst type makes adifferent type of polymer block, produces a linear block copolymer withthree different block types. Furthermore, if the ratio of the shuttlingrate to the propagation rate for the three catalysts follows the order1>2>3, then the average block length for the three block types willfollow the order 3>2>1, and there will be fewer instances of 2-typeblocks adjacent to 3-type blocks than 1-type blocks adjacent to 2-typeblocks.

It follows that a method exists for controlling the block lengthdistribution of the various block types. For example, by selectingcatalysts 1, 2, and 3 (wherein 2 and 3 produce substantially the samepolymer block type), and a chain shuttling agent, and the shuttling ratefollows the order 1>2 >3, the resulting polymer will have a bimodaldistribution of block lengths made from the 2 and 3 catalysts.

During the polymerization, the reaction mixture comprising the monomerto be polymerized is contacted with the activated catalyst compositionaccording to any suitable polymerization conditions. The process ischaracterized by use of elevated temperatures and pressures. Hydrogenmay be employed as a chain transfer agent for molecular weight controlaccording to known techniques if desired. As in other similarpolymerizations, it is highly desirable that the monomers and solventsemployed be of sufficiently high purity that catalyst deactivation doesnot occur. Any suitable technique for monomer purification such asdevolatilization at reduced pressure, contacting with molecular sievesor high surface area alumina, or a combination of the foregoingprocesses may be employed. The skilled artisan will appreciate that theratio of chain shuttling agent to one or more catalysts and or monomersin the process of the present invention may be varied in order toproduce polymers differing in one or more chemical or physicalproperties.

Supports may be employed in the present invention, especially in slurryor gas-phase polymerizations. Suitable supports include solid,particulated, high surface area, metal oxides, metalloid oxides, ormixtures thereof (interchangeably referred to herein as an inorganicoxide). Examples include: tale, silica, alumina, magnesia, titania,zirconia, Sn₂O₃, aluminosilicates, borosilicates, clays, and mixturesthereof. Suitable supports preferably have a surface area as determinedby nitrogen porosimetry using the B.E.T. method from 10 to 1000 m²/g,and preferably from 100 to 600 m²/g. The average particle size typicallyis from 0.1 to 500 m, preferably from 1 to 200 μm, more preferably 10 to100 μm.

In one embodiment of the invention the present catalyst composition andoptional support may be spray dried or otherwise recovered in solid,particulated form to provide a composition that is readily transportedand handled. Suitable methods for spray drying a liquid containingslurry are well known in the art and usefully employed herein. Preferredtechniques for spray drying catalyst compositions for use herein aredescribed in U.S. Pat. Nos. 5,648,310 and 5,672,669.

The polymerization is desirably carried out as a continuouspolymerization, preferably a continuous, solution polymerization, inwhich catalyst components, shuttling agent(s), monomers, and optionallysolvent, adjuvants, scavengers, and polymerization aids are continuouslysupplied to the reaction zone and polymer product continuously removedthere from. Within the scope of the terms “continuous” and“continuously” as used in this context are those processes in whichthere are intermittent additions of reactants and removal of products atsmall regular or irregular intervals, so that, over time, the overallprocess is substantially continuous.

The catalyst compositions can be advantageously employed in a highpressure, solution, slurry, or gas phase polymerization process. For asolution polymerization process it is desirable to employ homogeneousdispersions of the catalyst components in a liquid diluent in which thepolymer is soluble under the polymerization conditions employed. Onesuch process utilizing an extremely fine silica or similar dispersingagent to produce such a homogeneous catalyst dispersion where either themetal complex or the cocatalyst is only poorly soluble is disclosed inU.S. Pat. No. 5,783,512. A solution process to prepare the novelpolymers of the present invention, especially a continuous solutionprocess is preferably carried out at a temperature between 80° C. and250° C., more preferably between 100° C. and 210° C., and mostpreferably between 110° C. and 210° C. A high pressure process isusually carried out at temperatures from 100° C. to 400° C. and atpressures above 500 bar (50 MPa). A slurry process typically uses aninert hydrocarbon diluent and temperatures of from 0° C. up to atemperature just below the temperature at which the resulting polymerbecomes substantially soluble in the inert polymerization medium.Preferred temperatures in a slurry polymerization are from 30° C.,preferably from 60° C. up to 115° C., preferably up to 100° C. Pressurestypically range from atmospheric (100 kPa) to 500 psi (3.4 MPa).

In all of the foregoing processes, continuous or substantiallycontinuous polymerization conditions are preferably employed. The use ofsuch polymerization conditions, especially continuous, solutionpolymerization processes employing two or more active polymerizationcatalyst species, allows the use of elevated reactor temperatures whichresults in the economical production of multi-block or segmentedcopolymers in high yields and efficiencies. Both homogeneous andplug-flow type reaction conditions may be employed. The latterconditions are preferred where tapering of the block composition isdesired.

Both catalyst compositions (A) and (B) may be prepared as a homogeneouscomposition by addition of the requisite metal complexes to a solvent inwhich the polymerization will be conducted or in a diluent compatiblewith the ultimate reaction mixture. The desired cocatalyst or activatorand the shuttling agent may be combined with the catalyst compositioneither prior to, simultaneously with, or after combination with themonomers to be polymerized and any additional reaction diluent.

At all times, the individual ingredients as well as any active catalystcomposition must be protected from oxygen and moisture. Therefore, thecatalyst components, shuttling agent and activated catalysts must beprepared and stored in an oxygen and moisture free atmosphere,preferably a dry, inert gas such as nitrogen.

Without limiting in any way the scope of the invention, one means forcarrying out such a polymerization process is as follows. In astirred-tank reactor, the monomers to be polymerized are introducedcontinuously together with any solvent or diluent. The reactor containsa liquid phase composed substantially of monomers together with anysolvent or diluent and dissolved polymer. Preferred solvents includeC₄₋₁₀ hydrocarbons or mixtures thereof, especially alkanes such ashexane or mixtures of alkanes, as well as one or more of the monomersemployed in the polymerization.

Catalysts (A) and (B) along with cocatalyst and chain shuttling agentare continuously or intermittently introduced in the reactor liquidphase or any recycled portion thereof. The reactor temperature andpressure may be controlled by adjusting the solvent/monomer ratio, thecatalyst addition rate, as well as by cooling or heating coils, jacketsor both. The polymerization rate is controlled by the rate of catalystaddition. The ethylene content of the polymer product is determined bythe ratio of ethylene to comonomer in the reactor, which is controlledby manipulating the respective feed rates of these components to thereactor. The polymer product molecular weight is controlled, optionally,by controlling other polymerization variables such as the temperature,monomer concentration, or by the previously mentioned chain transferagent, as is well known in the art. Upon exiting the reactor, theeffluent is contacted with a catalyst kill agent such as water, steam oran alcohol. The polymer solution is optionally heated, and the polymerproduct is recovered by flashing off gaseous monomers as well asresidual solvent or diluent at reduced pressure, and, if necessary,conducting further devolatilization in equipment such as adevolatilizing extruder. In a continuous process the mean residence timeof the catalyst and polymer in the reactor generally is from 5 minutesto 8 hours, and preferably from 10 minutes to 6 hours.

Alternatively, the foregoing polymerization may be carried out in acontinuous loop reactor with or without a monomer, catalyst or shuttlingagent gradient established between differing regions thereof, optionallyaccompanied by separated addition of catalysts and/or chain transferagent, and operating under adiabatic or non-adiabatic solutionpolymerization conditions or combinations of the foregoing reactorconditions. Examples of suitable loop reactors and a variety of suitableoperating conditions for use therewith are found in U.S. Pat. Nos.5,977,251, 6,319,989 and 6,683,149.

Although not as desired, the catalyst composition may also be preparedand employed as a heterogeneous catalyst by adsorbing the requisitecomponents on an inert inorganic or organic particulated solid, aspreviously disclosed. In an preferred embodiment, a heterogeneouscatalyst is prepared by co-precipitating the metal complex and thereaction product of an inert inorganic compound and an active hydrogencontaining activator, especially the reaction product of a tri (C₁₋₄alkyl) aluminum compound and an ammonium salt of ahydroxyaryltris(pentafluorophenyl)borate, such as an ammonium salt of(4-hydroxy-3,5-ditertiarybutylphenyl)tris(pentafluorophenyl)borate. Whenprepared in heterogeneous or supported form, the catalyst compositionmay be employed in a slurry or a gas phase polymerization. As apractical limitation, slurry polymerization takes place in liquiddiluents in which the polymer product is substantially insoluble.Preferably, the diluent for slurry polymerization is one or morehydrocarbons with less than 5 carbon atoms. If desired, saturatedhydrocarbons such as ethane, propane or butane may be used in whole orpart as the diluent.

Preferably for use in gas phase polymerization processes, the supportmaterial and resulting catalyst has a median particle diameter from 20to 200 μm, more preferably from 30 μm to 150 μm, and most preferablyfrom 50 μm to 100 μm. Preferably for use in slurry polymerizationprocesses, the support has a median particle diameter from 1 μm to 200μm, more preferably from 5 μm to 100 μm, and most preferably from 10 μmto 80 μm.

Suitable gas phase polymerization process for use herein aresubstantially similar to known processes used commercially on a largescale for the manufacture of polypropylene, ethylene/α-olefincopolymers, and other olefin polymers. The gas phase process employedcan be, for example, of the type which employs a mechanically stirredbed or a gas fluidized bed as the polymerization reaction zone.Preferred is the process wherein the polymerization reaction is carriedout in a vertical cylindrical polymerization reactor containing afluidized bed of polymer particles supported or suspended above aperforated plate or fluidization grid, by a flow of fluidization gas.

The gas employed to fluidize the bed comprises the monomer or monomersto be polymerized, and also serves as a heat exchange medium to removethe heat of reaction from the bed. The hot gases emerge from the top ofthe reactor, normally via a tranquilization zone, also known as avelocity reduction zone, having a wider diameter than the fluidized bedand wherein fine particles entrained in the gas stream have anopportunity to gravitate back into the bed. It can also be advantageousto use a cyclone to remove ultra-fine particles from the hot gas stream.The gas is then normally recycled to the bed by means of a blower orcompressor and one or more heat exchangers to strip the gas of the heatof polymerization.

A preferred method of cooling of the bed, in addition to the coolingprovided by the cooled recycle gas, is to feed a volatile liquid to thebed to provide an evaporative cooling effect, often referred to asoperation in the condensing mode. The volatile liquid employed in thiscase can be, for example, a volatile inert liquid, for example, asaturated hydrocarbon having 3 to 8, preferably 4 to 6, carbon atoms. Inthe case that the monomer or comonomer itself is a volatile liquid, orcan be condensed to provide such a liquid, this can suitably be fed tothe bed to provide an evaporative cooling effect. The volatile liquidevaporates in the hot fluidized bed to form gas which mixes with thefluidizing gas. If the volatile liquid is a monomer or comonomer, itwill undergo some polymerization in the bed. The evaporated liquid thenemerges from the reactor as part of the hot recycle gas, and enters thecompression/heat exchange part of the recycle loop. The recycle gas iscooled in the heat exchanger and, if the temperature to which the gas iscooled is below the dew point, liquid will precipitate from the gas.This liquid is desirably recycled continuously to the fluidized bed. Itis possible to recycle the precipitated liquid to the bed as liquiddroplets carried in the recycle gas stream. This type of process isdescribed, for example in EP-89691; U.S. Pat. No. 4,543,399; WO-94/25495and U.S. Pat. No. 5,352,749. A particularly preferred method ofrecycling the liquid to the bed is to separate the liquid from therecycle gas stream and to reinject this liquid directly into the bed,preferably using a method which generates fine droplets of the liquidwithin the bed. This type of process is described in WO-94/28032.

The polymerization reaction occurring in the gas fluidized bed iscatalyzed by the continuous or semi-continuous addition of catalystcomposition according to the invention. The catalyst composition may besubjected to a prepolymerization step, for example, by polymerizing asmall quantity of olefin monomer in a liquid inert diluent, to provide acatalyst composite comprising supported catalyst particles embedded inolefin polymer particles as well.

The polymer is produced directly in the fluidized bed by polymerizationof the monomer or mixture of monomers on the fluidized particles ofcatalyst composition, supported catalyst composition or prepolymerizedcatalyst composition within the bed. Start-up of the polymerizationreaction is achieved using a bed of preformed polymer particles, whichare preferably similar to the desired polymer, and conditioning the bedby drying with inert gas or nitrogen prior to introducing the catalystcomposition, the monomers and any other gases which it is desired tohave in the recycle gas stream, such as a diluent gas, hydrogen chaintransfer agent, or an inert condensable gas when operating in gas phasecondensing mode. The produced polymer is discharged continuously orsemi-continuously from the fluidized bed as desired.

The gas phase processes most suitable for the practice of this inventionare continuous processes which provide for the continuous supply ofreactants to the reaction zone of the reactor and the removal ofproducts from the reaction zone of the reactor, thereby providing asteady-state environment on the macro scale in the reaction zone of thereactor. Products are readily recovered by exposure to reduced pressureand optionally elevated temperatures (devolatilization) according toknown techniques. Typically, the fluidized bed of the gas phase processis operated at temperatures greater than 50° C., preferably from 60° C.to 110° C., more preferably from 70° C. to Examples of gas phaseprocesses which are adaptable for use in the process of this inventionare disclosed in U.S. Pat. Nos. 4,588,790; 4,543,399; 5,352,749;5,436,304; 5,405,922; 5,462,999; 5,461,123; 5,453,471; 5,032,562;5,028,670; 5,473,028; 5,106,804; 5,556,238; 5,541,270; 5,608,019; and5,616,661.

As previously mentioned, functionalized derivatives of multi-blockcopolymers are also included within the present invention. Examplesinclude metallated polymers wherein the metal is the remnant of thecatalyst or chain shuttling agent employed, as well as furtherderivatives thereof, for example, the reaction product of a metallatedpolymer with an oxygen source and then with water to form a hydroxylterminated polymer. In another embodiment, sufficient air or otherquench agent is added to cleave some or all of the shuttlingagent-polymer bonds thereby converting at least a portion of the polymerto a hydroxyl terminated polymer. Additional examples include olefinterminated polymers formed by β-hydride elimination and ethylenicunsaturation in the resulting polymer.

In one embodiment of the invention the multi-block copolymer may befunctionalized by maleation (reaction with maleic anhydride or itsequivalent), metallation (such as with an alkyl lithium reagent,optionally in the presence of a Lewis base, especially an amine, such astetramethyletlhylenediamine). Techniques for functionalization ofpolymers are well known, and disclosed for example in U.S. Pat. No.5,543,458, and elsewhere.

Because a substantial fraction of the polymeric product exiting thereactor is terminated with the chain shuttling agent, furtherfunctionalization is relatively easy. The metallated polymer species canbe utilized in well known chemical reactions such as those suitable forother alkyl-aluminum, alkyl-gallium, alkyl-zinc, or alkyl-Group 1compounds to form amine-, hydroxy-, epoxy-, ketone-, ester-, nitrile-,and other functionalized terminated polymer products. Examples ofsuitable reaction techniques that are adaptable for use here in aredescribed in Negishi, “Orgaonmetallics in Organic Synthesis”, Vol. 1 and2, (1980), and other standard texts in organometallic and organicsynthesis.

Polymer Products

Utilizing the present process, novel polymers, including multi-blockcopolymers, are readily prepared. Highly desirably, the polymers areinterpolymers comprising in polymerized form ethylene, having blocks ofsegments characterized by the presence of hyper-branching and othersegments of highly crystalline polyethylene.

The multi-block copolymers of the invention are believed to becharacterized by the presence of differentiated blocks within thepolymer chains, having both crystalline and amorphous nature. Thepresence of such differentiated blocks in the interpolymers of theinvention can be identified by unique TREF elution curves as well asATREFF or other standard analytical techniques.

In the various embodiments of the invention, unless indicated otherwise,the inventive polymers preferably possess a heat of fusion of 130 J/g orless, an ethylene content (that is —CH₂—CH₂polymer segments) of at least50 weight percent, preferably at least 90 percent, a glass transitiontemperature, T_(g), of less than −25° C., more preferably less than −30°C., and/or one and only one T_(m).

Additionally, the polymers of the invention can have a melt index, I₂,from 0.01 to 2000 g/10 minutes, preferably from 0.01 to 1000 g/10minutes, more preferably from 0.01 to 500 g/10 minutes, and especiallyfrom 0.01 to 100 g/10 minutes. Desirably, the invented polymers can havemolecular weights, M_(w), from 1,000 g/mole to 5,000,000 g/mole,preferably from 1000 g/mole to 1,000,000, more preferably from 10000g/mole to 500,000 g/mole, and especially from 10,000 g/mole to 300,000g/mole. The density of the invented polymers can be from 0.80 to 0.99g/cm³ and preferably for ethylene containing polymers from 0.85 g/cm³ to0.97 g/cm³.

Moreover, the present polymers may be prepared using techniques toinfluence the degree or level of blockiness. That is the amount ofbranching and length of each polymer block or segment can be altered bycontrolling the ratio and type of catalysts and shuttling agent as wellas the temperature of the polymerization, and other polymerizationvariables. A surprising benefit of this phenomenon is the discovery thatas the degree of blockiness is increased, the optical properties, tearstrength, and high temperature recovery properties of the resultingpolymer are improved. In particular, haze decreases while clarity, tearstrength, and high temperature recovery properties increase as theaverage number of blocks in the polymer increases. By selectingshuttling agents and catalyst combinations having the desired chaintransferring ability (high rates of shuttling with low levels of chaintermination) other forins of polymer termination are effectivelysuppressed. Accordingly, little if any β-hydride elimination is observedin the polymerization according to the invention, and the resultingcrystalline blocks are highly, or substantially completely, linear,possessing little or no long chain branching.

Another surprising benefit of the invention is that polymers whereinchain ends are highly crystalline can be selectively prepared. Incertain applications, reducing the relative quantity of polymer thatterminates with an amorphous block reduces the intermolecular dilutiveeffect on crystalline regions. This result can be obtained by choosingchain shuttling agents and catalysts having an appropriate response tohydrogen or other chain terminating agents. Specifically, if thecatalyst which produces highly crystalline polymer is more susceptibleto chain termination (such as by use of hydrogen) than the catalystresponsible for producing the less crystalline polymer segment (such asthrough chain walking or long chain branched polymer formation), thenthe highly crystalline polymer segments will preferentially populate theterminal portions of the polymer. Not only are the resulting terminatedgroups crystalline, but upon termination, the highly crystalline polymerforming catalyst site is once again available for reinitiation ofpolymer formation. The initially formed polymer is therefore anotherhighly crystalline polymer segment. Accordingly, both ends of theresulting multi-block copolymer are preferentially highly crystalline.

Additional components of the present formulations usefully employedaccording to the present invention include various other ingredients inamounts that do not detract from the properties of the resultantcomposition. These ingredients include, but are not limited to,activators such as calcium or magnesium oxide; fatty acids such asstearic acid and salts thereof; fillers and reinforcers such as calciumor magnesium carbonate, silica, and aluminum silicates; plasticizerssuch as dialkyl esters of dicarboxylic acids; antidegradants; softeners;waxes; and pigments.

Applications and End Uses

The polymers of the invention can be useful employed in a variety ofconventional thermoplastic fabrication processes to produce usefularticles, including objects comprising at least one film layer, such asa monolayer film, or at least one layer in a multilayer film prepared bycast, blown, calendered, or extrusion coating processes; moldedarticles, such as blow molded, injection molded, or rotomolded articles;extrusions; fibers; and woven or non-woven fabrics. Thermoplasticcompositions comprising the present polymers, include blends with othernatural or synthetic polymers, additives, reinforcing agents, ignitionresistant additives, antioxidants, stabilizers, colorants, extenders,crosslinkers, blowing agents, and plasticizers. Of particular utilityare multi-component fibers such as core/sheath fibers, having an outersurface layer, comprising at least in part, one or more polymers of theinvention.

Fibers that may be prepared from the present polymers or blends includestaple fibers, tow, multicomponent, sheath/core, twisted, andmonofilament. Suitable fiber forming processes include spinbonded, meltblown techniques, as disclosed in U.S. Pat. Nos. 4,430,563, 4, 663,220,4,668,566, and 4,322,027, gel spun fibers as disclosed in U.S. Pat. No.4,413,110, woven and nonwoven fabrics, as disclosed in U.S. Pat. No.3,485,706, or structures made from such fibers, including blends withother fibers, such as polyester, nylon or cotton, thermoformed articles,extruded shapes, including profile extrusions and co-extrusions,calendared articles, and drawn, twisted, or crimped yarns or fibers. Thenew polymers described herein are also useful for wire and cable coatingoperations, as well as in sheet extrusion for vacuum forming operations,and forming molded articles, including the use of injection molding,blow molding process, or rotomolding processes. Compositions comprisingthe polymers of the present invention can also be formed into fabricatedarticles such as those previously mentioned using conventionalpolyolefin processing techniques which are well known to those skilledin the art of polyolefin processing.

Dispersions (both aqueous and non-aqueous) can also be formed using thepresent polymers or formulations comprising the same. Frothed foamscomprising the invented polymers can also be formed, as disclosed in PCTapplication No. 2004/027593, filed Aug. 25, 2004. The polymers may alsobe crosslinked by any known means, such as the use of peroxide, electronbean, silane, azide, or other cross-linking technique. The polymers canalso be chemically modified, such as by grafting (for example by use ofmaleic anhydride (MAH), silanes, or other grafting agent), halogenation,amination, sulfonation, or other chemical modification.

Additives and adjuvants may be included in any formulation comprisingthe present polymers. Suitable additives include fillers, such asorganic or inorganic particles, including clays, talc, carbon black,titanium dioxide, zeolites, powdered metals, organic or inorganicfibers, including carbon fibers, silicon nitride fibers, steel wire ormesh, and nylon or polyester cording, nano-sized particles, clays, andso forth; tackifiers, oil extenders, including paraffinic or napthelenicoils; and other natural and synthetic polymers, including other polymersaccording to the invention.

Suitable polymers for blending with the polymers of the inventioninclude thermoplastic and non-thermoplastic polymers including naturaland synthetic polymers. Exemplary polymers for blending includepolypropylene, (both impact modifying polypropylene, isotacticpolypropylene, atactic polypropylene, and random ethylene/propylenecopolymers), various types of polyethylene, including high pressure,free-radical LDPE, Ziegler Natta LLDPE, metallocene PE, includingmultiple reactor PE (“in reactor” blends of Ziegler-Natta PE andmetallocene PE, such as products disclosed in U.S. Pat. Nos. 6,545,088,6,538,070, 6,566,446, 5,844,045, 5,869,575, and 6,448,341,ethylene-vinyl acetate (EVA), ethylene/vinyl alcohol copolymers,polystyrene, impact modified polystyrene, ABS, styrene/butadiene blockcopolymers and hydrogenated derivatives thereof (SBS and SEBS), andthermoplastic polyurethanes. Homogeneous polymers such as olefinplastomers and elastomers, ethylene and propylene-based copolymers (forexample polymers available under the trade designation VERSIFY™available from The Dow Chemical Company and VISTAMAXX™ available fromExxonMobil can also be useful as components in blends comprising thepresent polymers.

Suitable end uses for the foregoing products include elastic films andfibers; soft touch goods, such as tooth brush handles and appliancehandles; gaskets and profiles; adhesives (including hot melt adhesivesand pressure sensitive adhesives); footwear (including shoe soles andshoe liners); auto interior parts and profiles; foam goods (both openand closed cell); impact modifiers for other thermoplastic polymers suchas high density polyethylene, isotactic polypropylene, or other olefinpolymers; coated fabrics; hoses; tubing; weather stripping; cap liners;flooring; and viscosity index modifiers, also known as pour pointmodifiers, for lubricants.

In a highly desired embodiment of the invention thermoplasticcompositions comprising a thermoplastic matrix polymer, especiallyisotactic polypropylene, and an elastomeric multi-block copolymer ofethylene and a copolymerizable comonomer according to the invention, areuniquely capable of forming core-shell type particles having hardcrystalline or semi-crystalline blocks in the form of a core surroundedby soft or elastomeric blocks forming a “shell” around the occludeddomains of hard polymer. These particles are formed and dispersed withinthe matrix polymer by the forces incurred during melt compounding orblending. This highly desirable morphology is believed to result due tothe unique physical properties of the multi-block copolymers whichenable compatible polymer regions such as the matrix and highercomonomer content elastomeric regions of the multi-block copolymer toself-assemble in the melt due to thermodynamic forces. Shearing forcesduring compounding are believed to produce separated regions of matrixpolymer encircled by elastomer. Upon solidifying, these regions becomeoccluded elastomer particles encased in the polymer matrix.

Particularly desirable blends are thermoplastic polyolefin blends (TPO),thermoplastic elastomer blends (TPE), thermoplastic vulcanisites (TPV)and styrenic polymer blends. TPE and TPV blends may be prepared bycombining the invented multi-block polymers, including functionalized orunsaturated derivatives thereof with an optional rubber, includingconventional block copolymers, especially an SBS block copolymer, andoptionally a crosslinking or vulcanizing agent. TPO blends are generallyprepared by blending the invented multi-block copolymers with apolyolefin, and optionally a crosslinking or vulcanizing agent. Theforegoing blends may be used in forming a molded object, and optionallycrosslinking the resulting molded article. A similar procedure usingdifferent components has been previously disclosed in U.S. Pat. No.6,797,779.

Suitable conventional block copolymers for this application desirablypossess a Mooney viscosity (ML 1+4 @ 100° C.) in the range from 10 to135, more preferably from 25 to 100, and most preferably from 30 to 80.Suitable polyolefins especially include linear or low densitypolyethylene, polypropylene (including atactic, isotactic, syndiotacticand impact modified versions thereof) and poly(4-methyl-1-pentene).Suitable styrenic polymers include polystyrene, rubber modifiedpolystyrene (HIPS), styrene/acrylonitrile copolymers (SAN), rubbermodified SAN (ABS or AES) and styrene maleic anhydride copolymers.

The blends may be prepared by mixing or kneading the respectivecomponents at a temperature around or above the melt point temperatureof one or both of the components. For most multiblock copolymers, thistemperature may be above 130° C., most generally above 145° C., and mostpreferably above 150° C. Typical polymer mixing or kneading equipmentthat is capable of reaching the desired temperatures and meltplastifying the mixture may be employed. These include mills, kneaders,extruders (both single screw and twin-screw), Banbury mixers, calenders,and the like. The sequence of mixing and method may depend on the finalcomposition. A combination of Banbury batch mixers and continuous mixersmay also be employed, such as a Banbury mixer followed by a mill mixerfollowed by an extruder. Typically, a TPE or TPV composition will have ahigher loading of cross-linkable polymer (typically the conventionalblock copolymer containing unsaturation) compared to TPO compositionsGenerally, for TPE and TPV compositions, the weight ratio of blockcopolymer to multi-block copolymer maybe from about 90:10 to 10:90, morepreferably from 80:20 to 20:80, and most prefexably from 75:25 to 25:75.For TPO applications, the weight ratio of multi-block copolymer topolyolefin may be from about 49:51 to about 5:95, more preferably from35:65 to about 10:90. For modified styrenic polymer applications, theweight ratio of multi-block copolymer to polyolefin may also be fromabout 49:51 to about 5:95, more preferably from 35:65 to about 10:90.The ratios may be changed by changing the viscosity ratios of thevarious components. There is considerable literature illustratingtechniques for changing the phase continuity by changing the viscosityratios of the constituents of a blend and a person skilled in this artmay consult if necessary.

The blend compositions may contain processing oils, plasticizers, andprocessing aids. Rubber processing oils have a certain ASTM designationsand paraffinic, napthenic or aromatic process oils are all suitable foruse. Generally from 0 to 150 parts, Bore preferably 0 to 100 parts, andmost preferably from 0 to 50 parts of oil per 100 parts of total polymerare employed. Higher amounts of oil may tend to improve the processingof the resulting p product at the expense of some physical properties.Additional processing aids include conventional waxes, fatty acid salts,such as calcium stearate or zinc stearate, (poly)alcohols includingglycols, (poly)alcohol ethers, including glycol ethers, (poly)esters,including (poly)glycol esters, and metal s salt-, especially Group 1 or2 metal or zinc-, salt derivatives thereof.

It is known that non-hydrogenated rubbers such as those comprisingpolymerized forms of butadiene or isoprene, including block copolymers(here-in-after diene rubbers), have lower resistance to UV, ozone, andoxidation, compared to mostly or highly saturated rubbers. Inapplications such as tires made from compositions containing higherconcentrations of diene based rubbers, it is known to incorporate carbonblack to improve rubber stability, along with anti-ozone additives andanti-oxidants. Multi-block copolymers according to the present inventionpossessing extremely low levels of unsaturation, find particularapplication as a protective surface layer (coated, coextruded orlaminated) or weather resistant film adhered to articles formed fromconventional diene elastomer modified polymeric compositions.

For conventional TPO, TPV, and TPE applications, carbon black is theadditive of choice for UV absorption and stabilizing properties.Representative examples of carbon blacks include ASTM N110, N121, N220,N231, N234, N242, N293, N299, S315, N326, N330, M332, N339, N343, N347,N351, N358, N375, N539, N550, N582, N630, N642, N650, N683, N754, N762,N765, N774, N787, N907, N908, N990 and N991. These carbon blacks haveiodine absorptions ranging from 9 to 145 g/kg and average pore volumesranging from 10 to 150 cm³/100 g. Generally, smaller particle sizedcarbon blacks are employed, to the extent cost considerations permit.For many such applications the present multi-block copolymers and blendsthereof require little or no carbon black, thereby allowing considerabledesign freedom to include alternative pigments or no pigments at all.Multi-hued tires or tires matching the color of the vehicle are onepossibility.

Compositions, including thermoplastic blends according to the inventionmay also contain anti-ozonants or anti-oxidants that are known to arubber chemist of ordinary skill. The anti-ozonants may be physicalprotectants such as waxy materials that come to the surface and protectthe part from oxygen or ozone or they may be chemical protectors thatreact with oxygen or ozone. Suitable chemical protectors includestyrenated phenols, butylated octylated phenol, butylateddi(dimethylbenzyl) phenol, p-phenylenediamines, butylated reactionproducts of p-cresol and dicyclopentadiene (DCPD), polyphenolicanitioxidants, hydroquinone derivatives, quinoline, diphenyleneantioxidants, thioester antioxidants, and blends thereof. Somerepresentative trade names of such products are Wingstay™ S antioxidant,Polystay™ 100 antioxidant, Polystay™ 100 AZ antioxidant, Polystay™ 200antioxidant, Wingstay™ L antioxidant, Wingstay™ LHLS antioxidant,Wingstay™ K antioxidant, Wingstay™ 29 antioxidant, Wingstay™ SN-1antioxidant, and Irganox™ antioxidants. In some applications, theanti-oxidants and anti-ozonants used will preferably be non-staining andnon-migratory.

For providing additional stability against UV radiation, hindered aminelight stabilizers (HALS) and UV absorbers may be also used. Suitableexamples include Tinuvin™ 123, Tinuvin™ 144, Tinuvin™ 622, Tinuvin™ 765,Tinuvin™ 770, and Tinuvin™ 780, available from Ciba Specialty Chemicals,and Chemisorb™ T944, available from Cytex Plastics, Houston Tex., USA. ALewis acid may be additionally included with a HALS compound in order toachieve superior surface quality, as disclosed in U.S. Pat. No.6,051,681.

For some compositions, additional mixing process may be employed topre-disperse the anti-oxidants, anti-ozonants, carbon black, UVabsorbers, and/or light stabilizers to form a masterbatch, andsubsequently to form polymer blends there from.

Suitable crosslinking agents (also referred to as curing or vulcanizingagents) for use herein include sulfur based, peroxide based, or phenolicbased compounds. Examples of the foregoing materials are found in theart, including in U.S. Pat. Nos. 3,758,643, 3,806,558, 5,051,478,4,104,210, 4,130,535, 4,202,801, 4,271,049, 4,340,684, 4,250,273,4,927,882, 4,311,628 and 5,248,729.

When sulfur based curing agents are employed, accelerators and cureactivators may be used as well. Accelerators are used to control thetime and/or temperature required for dynamic vulcanization and toimprove the properties of the resulting cross-linked article. In oneembodiment, a single accelerator or primary accelerator is used. Theprimary accelerator(s) may be used in total amounts ranging from about0.5 to about 4, preferably about 0.8 to about 1.5, phr, based on totalcomposition weight. In another embodiment, combinations of a primary anda secondary accelerator might be used with the secondary acceleratorbeing used in &smaller amounts, such as from about 0.05 to about 3 phr,in order to activate and to improve the properties of the cured article.Combinations of accelerators generally produce articles havingproperties that are somewhat better than those produced by use of asingle accelerator. In addition, delayed action accelerators may be usedwhich are not affected by normal processing temperature s yet produce asatisfactory cure at ordinary vulcanization temperatures. Vulcanizationretarders might also be used. Suitable types of accelerators that may beused in the present invention are amines, disulfides, guanidines,thioureas, thiazoles, thiurams, sulfenamides, dithiocarbaniates andxanthates. Preferably, the primary accelerator is a sulfenamide. If asecond accelerator is used, the secondary accelerator is preferably aguanidine, dithiocarbarnate or thiuram compound. Certain processing aidsand cure activators such as stearic acid and ZnO may also be used. Whenperoxide based curing agents are used, co-activators or coagents may beused in combination therewith. Suitable coagents includetrimethylolpropane triacrylate (TMPTA), trimethylolpropanetrimethacrylate (TMPTMA), triallyl cyanurate (TAC), triallylisocyanurate (TAIC), among others. Use of peroxide crosslinkers andoptional coagents used for partial or complete dynamic vulcanization areknown in the art and disclosed for example in the publication, “PeroxideVulcanization of El astomer”, Vol. 74, No 3, July-August 2001.

When the multi-block copolymer containing composition is at leastpartially crosslinked, the degree of crosslinking may be measured bydissolving the composition in a solvent for specified duration, andcalculating the percent gel or unextractable component. The percent gelnormally increases with increasing crosslinking levels. For curedarticles according to the invention, the percent gel content isdesirably in the range from 5 to 100 percent.

The multi-block copolymers of the invention as well as blends thereofpossess improved processability compared to prior art compositions, due,it is believed, to lower melt viscosity. Thus, the composition or blenddemonstrates an improved surface appearance, especially when formed intoa molded or extruded article. At the same time, the present compositionsand -blends thereof uniquely possess improved melt strength properties,thereby allowing the present multi-block copolymers and blends thereof,especially TPO blends, to be usefully employed in foam and thermoformingapplications where melt strength is currently inadequate.

Thermoplastic compositions according to the invention may also containorganic or inorganic fillers or other additives such as starch, talc,calcium carbonate, glass fibers, polymeric fibers (including nylon,rayon, cotton, polyester, and polyaramide), metal fibers, flakes orparticles, expandable layered silicates, phosphates or carbonates, suchas clays, mica, silica, alumina, aluminosilicates or aluminophosphates,carbon whiskers, carbon fibers, nanoparticles including nanotubes,wollastonite, graphite, zeolites, and ceramics, such as siliconcarbi(Le, silicon nitride or titanias. Silane based or other couplingagents may also be employed for better filler bonding.

The thermoplastic compositions of this invention, including theforegoing blends, may be processed by conventional molding techniquessuch as injection molding, extrusion molding, thermoforming, slushmolding, over molding, insert molding, blow molding, and othertechniques. Films, including multi-layer films, may be produced by castor entering process , including blown film processes.

Testing Methods In the foregoing characterizing disclosure and theexamples that follow, the following analytical techniques are employed:

Standard CRYSTAF Method

Branching distributions are determined by crystallization analysisfractionation (CRYSTAF) using a CRYSTAF 200 unit commercially availablefrom PolymexChar, Valencia, Spain. The samples are dissolved in 1,2,4trichlorobenzene at 160° C. (0.66 mg/mL) for 1 hr and stabilized at 95°C. for 45 minutes. The sampling temperatures range from 95 to 30° C. ata cooling rate of 0.2° C./min. An infrared detector is used to measurethe polymer solution concentrations. The cumulative solubleconcentration is measured as the polymer crystallizes while thetemperature is decreased. The analytical derivative of the cumulativeprofile reflects the short chain branching distribution of the polymer.

The CRYSTAF peak temperature and area are identified by the peakanalysis module included in the CRYSTAF Software (Version 2001.b,PolymerChar, Valencia, Spain). The CRYSTAF peak finding routineidentifies a peak temperature as a maximum in the dW/dT and the areabetween the largest positive inflections on either side of theidentified peak in the derivative curve. To calculate the CRYSTAF curve,the preferred processing parameters are with a temperature limit of 70°C. and with smoothing parameters above the temperature limit of 0.1, andbelow the temperature limit of 0.3.

DSC Standard Method

Differential Scanning Calorimetry results are determined using a TAImodel Q1000 DSC equipped with an RCS cooling accessory and anautosampler. A nitrogen purge gas flow of 50 ml/min is used. The sampleis pressed into a thin film and melted in the press at about 175° C. andthen air-cooled to room temperature (25° C.). 3-10 mg Of material isthen cut into a 6 mm diameter disk, accurately weighed, placed in alight aluminum pan (ca 50 mg), and then crimped shut. The thermalbehavior of the sample is investigated with the following temperatureprofile. The sample is rapidly heated to 180° C. and held isothermal for3 minutes in order to remove any previous thermal history. The sample isthen cooled to −40° C. at 10° C./min cooling rate and held at −40° C.for 3 minutes. The sample is then heated to 150° C. at 10° C./min.heating rate. The cooling and second heating curves are recorded.

The DSC melting peak is measured as the maximum in heat flow rate (W/g)with respect to the linear baseline drawn between −30° C. and end ofmelting. The heat of fusion is measured as the area under the meltingcurve between −30° C. and the end of melting using a linear baseline.

Abrasion Resistance

Abrasion resistance is measured on compression molded plaques accordingto ISO 4649. The average value of 3 measurements is reported. Plaquesfor the test are 6.4 mm thick and compression molded using a hot press(Carver Model #4095-4PR1001R). The pellets are placed betweenpolytetrafluoroethylene sheets, heated at 190° C. at 55 psi (380 kPa)for 3 minutes, followed by 1.3 MPa for 3 minutes, and then 2.6 MPa for 3minutes. Next the plaques are cooled in the press with running coldwater at 1.3 MPa for 1 minute and removed for testing.

GPC Method

The gel permeation chromatographic system consists of either a PolymerLaboratories Model PL-210 or a Polymer Laboratories Model PL-220instrument. The column and carousel compartments are operated at 140° C.Three Polymer Laboratories 10-micron Mixed-B columns are used. Thesolvent is 1,2,4 trichlorobenzene. The samples are prepared at aconcentration of 0.1 grams of polymer in 50 milliliters of solventcontaining 200 ppm of butylated hydroxytoluene (BHT). Samples areprepared by agitating lightly for 2 hours at 160° C. The injectionvolume used is 100 microliters and the flow rate is 1.0 ml/minute.

Calibration of the GPC column set is performed with 21 narrow molecularweight distribution polystyrene standards with molecular weights rangingfrom 580 to 8,400,000, arranged in 6 “cocktail” mixtures with at least adecade of separation between individual molecular weights. The standardsare purchased from Polymer Laboratories (Shropshire, UK). Thepolystyrene standards are prepared at 0.025 grams in 50 milliliters ofsolvent for molecular weights equal to or greater than 1,000,000, and0.05 grams in 50 milliliters of solvent for molecular weights less than1,000,000. The polystyrene standards are dissolved at 80° C. with gentleagitation for 30 minutes. The narrow standards mixtures are run firstand in order of decreasing highest molecular weight component tominimize degradation. The polystyrene standard peak molecular weightsare converted to polyethylene molecular weights using the followingequation (as described in Williams and Ward, J. Polym. Sci., Polym.Let., 6, 621 (1968)): M_(polyethylene)=0.431 (M_(polystyrene)).

Polyetheylene equivalent molecular weight calculations are performedusing Viscotek TriSEC software Version 3.0.

Compression Set

Compression set is measured according to ASTM D 395. The sample isprepared by stacking 25.4 mm diameter round discs of 3.2 mm, 2.0 mm, and0.25 mm thickness until a total thickness of 12.7 mm is reached. Thediscs are cut from 12.7 cm×12.7 cm compression molded plaques moldedwith a hot press under the following conditions: zero pressure for 3 minat 190° C., followed by 86 MPa for 2 min at 190° C., followed by coolinginside the press with cold running water at 86 MPa.

Density

Samples for density measurement are prepared according to ASTM D 1928.Measurements are made within one hour of sample pressing using ASTMD792, Method B.

Flexural/Secant Modulus/Storage Modulus

Samples are compression molded using ASTM D 1928. Flexural and 2 percentsecant module are measured according to ASTM D-790. Storage modulus ismeasured according to ASTM D 5026-01 or equivalent technique.

Optical Properties

Films of 0.4 mm thickness are compression molded using a hot press(Carver Model #4095-4PR1001R). The pellets are placed betweenpolytetrafluoroethylene sheets, heated at 190° C. at 55 psi (380 kPa)for 3 min, followed by 1.3 MPa for 3 min, and then 2.6 MPa for 3 min.The film is then cooled in the press with running cold water at 1.3 MPafor 1 min. The compression molded films are used for opticalmeasurements, tensile behavior, recovery, and stress relaxation.

Clarity is measured using BYK Gardner Haze-guard as specified in ASTM D1746.

45° gloss is measured using BYK Gardner Glossmeter Microgloss 45° asspecified in ASTM D-2457

Internal haze is measured using BYK Gardner Haze-guard based on ASTM D1003 Procedure A. Mineral oil is applied to the film surface to removesurface scratches.

Mechanical Properties—Tensile, Hysteresis, and Tear

Stress-strain behavior in uniaxial tension is measured using ASTM D 1708microtensile specimens. Samples are stretched with an Insertion at 500%min⁻¹ at 21° C. Tensile strength and elongation at break are reportedfrom an average of 5 specimens.

100% and 300% Hysteresis is determined from cyclic loading to 100% and300% strains using ASTM D 1708 microtensile specimens with an Insertion™instrument. The sample is loaded and unloaded at 267% min⁻¹ for 3 cyclesat 21° C. Cyclic experiments at 300% and 80° C. are conducted using anenvironmental chamber. In the 80° C. experiment, the sample is allowedto equilibrate for 45 minutes at the test temperature before testing. Inthe 21° C., 300% strain cyclic experiment, the retractive stress at 150%strain from the first unloading cycle is recorded. Percent recovery forall experiments are calculated from the first unloading cycle using thestrain at which the load returned to the base line. The percent recoveryis defined as:${\%\quad{Recovery}} = {\frac{ɛ_{f} - ɛ_{s}}{ɛ_{f}} \times 100}$where ε_(f) is the strain taken for cyclic loading and ε_(s) is thestrain where the load returns to the baseline during the 1^(st)unloading cycle.

Stress relaxation is measured at 50 percent strain and 37° C. for 12hours using an Insertion™ instrument equipped with an environmentalchamber. The gauge geometry was 76 mm×25 mm×0.4 mm. After equilibratingat 37° C. for 45 min in the environmental chamber, the sample wasstretched to 50% strain at 333% min⁻¹. Stress was recorded as a functionof time for 12 hours. The percent stress relaxation after 12 hours wascalculated using the formula:${\%\quad{Stress}\quad{Relaxation}} = {\frac{L_{0} - L_{12}}{L_{0}} \times 100}$where L₀ is the load at 50% strain at 0 time and L₁₂ is the load at 50percent strain after 12 hours.

Tensile notched tear experiments are carried out on samples having adensity of 0.88 g/cc or less using an Insertion™ instrument. Thegeometry consists of a gauge section of 76 mm×13 mm×0.4 mm with a 2 mmnotch cut into the sample at half the specimen length. The sample isstretched at 508 mm min⁻¹ at 21° C. until it breaks. The tear energy iscalculated as the area under the stress-elongation curve up to strain atmaximum load. An average of at least 3 specimens are reported.

TMA

Thermal Mechanical Analysis (Penetration Temperature) is conducted on 30mm diameter×3.3 mm thick, compression molded discs, formed at 180° C.and 10 MPa molding pressure for 5 minutes and then air quenched. Theinstrument used is a TMA 7, brand available from Perkin-Elmer. In thetest, a probe with 1.5 mm radius tip (P/N N519-0416) is applied to thesurface of the sample disc with 1N force. The temperature is raised at5° C./min from 25° C. The probe penetration distance is measured as afunction of temperature. The experiment ends when the probe haspenetrated 1 mm into the sample.

DMA

Dynamic Mechanical Analysis (DMA) is measured on compression moldeddisks formed in a hot press at 180° C. at 10 MPa pressure for 5 minutesand then water cooled in the press at 90° C./min. Testing is conductedusing an ARES controlled strain rheometer (TA instruments) equipped withdual cantilever fixtures for torsion testing.

A 1.5 mm plaque is pressed and cut in a bar of dimensions 32×12 mm. Thesample is clamped at both ends between fixtures separated by 10 mm (gripseparation ΔL) and subjected to successive temperature steps from −100°C. to 200° C. (5° C. per step). At each temperature the torsion modulusG′ is measured at an angular frequency of 10 rad/s, the strain amplitudebeing maintained between 0.1 percent and 4 percent to ensure that thetorque is sufficient and that the measurement remains in the linearregime.

An initial static force of 10 g is maintained (auto-tension mode) toprevent slack in the sample when thermal expansion occurs. As aconsequence, the grip separation ΔL increases with the temperature,particularly above the melting or softening point of the polymer sample.The test stops at the maximum temperature or when the gap between thefixtures reaches 65 mm.

Pellet Blocking Strength

Pellets (150 g) are loaded into a 2″ (5 cm) diameter hollow cylinderthat is made of two halves held together by a hose clamp. A 2.75 lb(1.25 kg) load is applied to the pellets in the cylinder at 45° C. for 3days. After 3 days, the pellets loosely consolidate into a cylindricalshaped plug. The plug is removed from the form and the pellet blockingforce measured by loading the cylinder of blocked pellets in compressionusing an Insertion™ instrument to measure the compressive force neededto break the cylinder into pellets.

Melt Index

Melt index, or I₂, is measured in accordance with ASTM D 1238, Condition190° C./2.16 kg. Melt index, or I₁₀ is also measured in accordance withASTM D 1238, Condition 190° C./10 kg.

ATREF

Analytical temperature rising elution fractionation (ATREF) analysis isconducted according to the method described in U.S. Pat. No. 4,798,081.The composition to be analyzed is dissolved in trichlorobenzene andallowed to crystallize in a column containing an inert support(stainless steel shot) by slowly reducing the temperature to 20° C. at acooling rate of 0.1° C./min. The column is equipped with an infrareddetector. An ATREF chromatogram curve is then generated by eluting thecrystallized polymer sample from the column by slowly increasing thetemperature of the eluting solvent (trichlorobenzene) from 20 to 120° C.at a rate of 1.5° C./min.

Polymer Fractionation by TREF

Large-scale TREF fractionation is carried by dissolving 15-20 g ofpolymer in 2 liters of 1,2,4-trichlorobenzene (TCB)by stirring for 4hours at 160° C. The polymer solution is forced by 15 psig (100 kPa)nitrogen onto a 3 inch by 4 foot (7.6 cm×12 cm) steel column packed witha 60:40 (v:v) mix of 30-40 mesh (600-425 μm) spherical, technicalquality glass beads (available from Potters Industries, HC 30 Box 20,Brownwood, Tex., 76801) and stainless steel, 0.028″ (0.7 mm) diametercut wire shot (available form Pellets, Inc. 63 Industrial Drive, NorthTonawanda, N.Y., 14120). The column is immersed in a thermallycontrolled oil jacket, set initially to 160° C. The column is firstcooled ballistically to 125° C., then slow cooled to 20° C. at 0.04° C.per minute and held for one hour. Fresh TCB is introduced at about 65ml/min while the temperature is increased at 0.167° C. per minute.

Approximately 2000 ml portions of eluant from the preparative TREFcolumn are collected in a 16 station, heated fraction collector. Thepolymer is concentrated in each fraction using a rotary evaporator untilabout 50 to 100 ml of the polymer solution remains. The concentratedsolutions are allowed to stand overnight before adding excess methanol,filtering, and rinsing (approx. 300-500 ml of methanol including thefinal rinse). The filtration step is performed on a 3 position vacuumassisted filtering station using, 5.0 μm polytetrafluoroethylene coatedfilter paper (available from Osmonics Inc., Cat# Z50WP04750). Thefiltrated fractions are dried overnight in a vacuum oven at 60° C. andweighed on an analytical balance before further testing.

¹³C NMR Analysis The samples are prepared by adding approximately 3 g ofa 50/50 mixture of tetrachloroethane-d²/orthodichlorobenzene to 0.4 gsample in a 10 mm NMR tube. The samples are dissolved and homogenized byheating the tube and its contents to 150° C. The data is collected usinga JEOL Eclipse™ 400 MHz spectrometer or a Varian Unity Plus™ 400 MHzspectrometer, corresponding to a ¹³C resonance frequency of 100.5 MHz.The data is acquired using 4000 transients per data file with a 6 secondpulse repetition delay. To achieve minimum signal-to-noise forquantitative analysis, multiple data files are added together. Thespectral width is 25,000 Hz with a minimum file size of 32K data points.The samples are analyzed at 130° C. in a 10 mm broad band probe. Thecomonomer incorporation is determined using Randall's triad method(Randall, J. C.; JMS-Rev. Macromol. Chem. Phys., C29, 201-317 (1989).

Atomic Force Microscopy (AFM)

Sections are collected from the sample material using a Leica UCT™microtome with a FC cryo-chainber operated at −80° C. A diamond knife isused to section all sample material to a thickness of 120 nm. Sectionsare placed on freshly cleaved mica surfaces, and mounted on standard AFMspecimen metal support disks with a double carbon tape. The sections areexamined with a DI NanoScope IV™ Multi-Mode AFM, in tapping mode withphase detection. Nano-sensor tips are used in all experiments.

SPECIFIC EMBODIMENTS

The following specific embodiments of the invention and combinationsthereof are especially desirable and hereby delineated in order toprovide detailed disclosure for the appended claims.

1. A composition comprising the admixture or reaction product resultingfrom combining:

(A) a first olefin polymerization catalyst,

(B) a second olefin polymerization catalyst capable of preparingpolymers differing in chemical or physical properties from the polymerprepared by catalyst (A) under equivalent polymerization conditions,

at least one of catalyst (A) or catalyst (B) being capable of forming abranched polymer by means of chain walking or reincorporation of in situformed olefinic polymer chains, and

(C) a chain shuttling agent.

2. A composition comprising the admixture or reaction product resultingfrom combining:

(A) a first olefin polymerization catalyst capable of forming a highlycrystalline ethylene homopolymers by ethylene polymerization;

(B) a second olefin polymerization catalyst capable of forming abranched polymer upon polymerization by means of chain walking orreincorporation of in situ formed olefinic polymer chains, and

(C) a chain shuttling agent.

3. A process for preparing a high molecular weight, multi-blockcopolymer comprising contacting ethylene under addition polymerizationconditions with a composition comprising:

the admixture or reaction product resulting from combining:

(A) a first olefin polymerization catalyst,

(B) a second olefin polymerization catalyst capable of preparingpolymers differing in chemical or physical properties from the polymerprepared by catalyst (A) under equivalent polymerization conditions,

at least one of catalyst (A) or catalyst (B) being capable of forming abranched polymer by means of chain walking or reincorporation of in situformed olefinic polymer chains, and

(C) a chain shuttling agent.

4. A process for preparing a high molecular weight, multi-blockcopolymer comprising contacting ethylene under addition polymerizationconditions with a composition comprising:

the admixture or reaction product resulting from combining:

(A) a first olefin polymerization catalyst capable of forming a highlycrystalline ethylene homopolymer by ethylene polymerization;

(B) a second olefin polymerization catalyst capable of forming abranched polymer upon polymerization by means of chain walking orreincorporation of in situ formed olefinic polymer chains, and

(C) a chain shuttling agent.

5. A multi-block copolymer formed from a reaction mixture consistingessentially of ethylene as the addition polymerizable monomer, saidcopolymer containing therein two or more, preferably three or moresegments or blocks differing in branching index, said copolymerpossessing a molecular weight distribution, Mw/Mn, of less than 3.0,more preferably less than 2.8.

6. A multi-block copolymer formed from a reaction mixture consistingessentially of ethylene as the addition polymerizable monomer, saidcopolymer containing therein two or more, preferably three or moresegments or blocks differing in branching index.

7. A multi-block copolymer according to embodiment 6 possessing amolecular weight distribution, Mw/Mn, of less than 3.0, more preferablyless than 2.8.

8. A functionalized derivative of the multi-block copolymer of any oneof embodiments 5-7.

9. A crosslinked derivative of a polymer according to any one ofembodiments 5-7.

10. A crosslinked derivative of a polymer according to embodiment 8.

11. A polymer according to any one of embodiments 5-7, or preparable bythe method of embodiment 3 or 4, or a composition comprising the same inthe form of a film, at least one layer of a multilayer film, at leastone layer of a laminated article, a foamed article, a fiber, a nonwovenfabric, an injection molded article, a blow molded article, aroto-molded article, or an adhesive.

12. A polymer according to embodiment 8 or a composition comprising thesame in the form of a film, at least one layer of a multilayer film, atleast one layer of a laminated article, a foamed article, a fiber, anonwoven fabric, an injection molded article, a blow molded article, aroto-molded article, or an adhesive.

13. A polymer according to embodiment 9 or a composition comprising thesame in the form of a film, at least one layer of a multilayer film, atleast one layer of a laminated article, a foamed article, a fiber, anonwoven fabric, an injection molded article, a blow molded article, aroto-molded article, or an adhesive.

14. A polymer according to embodiment 10 or a composition comprising thesame in the form of a film, at least one layer of a multilayer film, atleast one layer of a laminated article, a foamed article, a fiber, anonwoven fabric, an injection molded article, a blow molded article, aroto-molded article, or an adhesive.

15. A composition according to embodiment 1 or 2 wherein the shuttlingagent is a trihydrocarbyl aluminum- or dihydrocarbyl zinc-compoundcontaining from 1 to 12 carbons in each hydrocarbyl group.

16. A composition according to embodiment 15 wherein the shuttling agentis triethylaluminum or diethylzinc.

17. A composition according to embodiment 1 or 2 wherein catalyst (A)comprises a complex comprising a transition metal selected from Groups4-8 of the Periodic Table of the Elements and one or more delocalized,x-bonded ligands or polyvalent Lewis base ligands.

18. A composition according to embodiment 17 wherein catalyst (A)corresponds to the formula:

wherein:

R¹¹ is selected from alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl,aryl, and inertly substituted derivatives thereof containing from 1 to30 atoms not counting hydrogen or a divalent derivative thereof;

T¹ is a divalent bridging group of from 1 to 41 atoms other thanhydrogen, preferably 1 to 20 atoms other than hydrogen, and mostpreferably a mono- or di-C₁₋₂₀ hydrocarbyl substituted methylene orsilane group; and

R¹² is a C₅₋₂₀ heteroaryl group containing Lewis base functionality,especially a pyridin-2-yl- or substituted pyridin-2-yl group or adivalent derivative thereof;

M¹ is a Group 4 metal, preferably hafnium;

X¹ is an anionic, neutral or dianionic ligand group;

x′ is a number from 0 to 5 indicating the number of such X¹ groups; and

bonds, optional bonds and electron donative interactions are representedby lines, dotted lines and arrows respectively.

19. A composition according to embodiment 18 wherein catalyst (B)corresponds to the formula:

wherein

-   -   M² is a metal of Groups 4-10 of the Periodic Table of the        elements;    -   T² is a nitrogen, oxygen or phosphorus containing group;    -   X² is halo, hydrocarbyl, or hydrocarbyloxy;    -   t is one or two;    -   x″ is a number selected to provide charge balance;    -   and T² and N are linked by a bridging ligand.

20. A process according to embodiment 3 or 4 which is a continuousprocess.

21. A process according to embodiment 20 which is a solution process.

22. A process according to embodiment 21 wherein ethylene conversion inthe reactor is at least 92 percent.

22. A process according to embodiment 22 wherein the ethylene conversionin the reactor is at least 95 percent.

23. A process according to embodiment 20 wherein catalyst (A)corresponds to the formula:

wherein:

R¹¹ is selected from alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl,aryl, and inertly substituted derivatives thereof containing from 1 to30 atoms not counting hydrogen or a divalent derivative thereof;

T¹ is a divalent bridging group of from 1 to 41 atoms other thanhydrogen, preferably 1 to 20 atoms other than hydrogen, and mostpreferably a mono- or di-C₁₋₂₀ hydrocarbyl substituted methylene orsilane group; and

R¹² is a C₅₋₂₀ heteroaryl group containing Lewis base functionality,especially a pyridin-2-yl- or substituted pyridin-2-yl group or adivalent derivative thereof;

M¹ is a Group 4 metal, preferably hafnium;

X¹ is an anionic, neutral or dianionic ligand group;

x′ is a number from 0 to 5 indicating the number of such X¹ groups; and

bonds, optional bonds and electron donative interactions are representedby lines, dotted lines and arrows respectively.

24. A process according to embodiment 23 wherein catalyst (B)corresponds to the formula:

wherein

-   -   M² is a metal of Groups 4-10 of the Periodic Table of the        elements;    -   T² is a nitrogen, oxygen or phosphorus containing group;    -   X² is halo, hydrocarbyl, or hydrocarbyloxy;    -   t is one or two;    -   x″ is a number selected to provide charge balance;    -   and T² and N are linked by a bridging ligand.

25. A process according to embodiment 3 or 4 in which the ratio of chainshuttling agent to one or more catalysts and or monomers is varied inorder to produce polymers differing in one or more chemical or physicalproperties.

26. A polymer mixture comprising: (1) an organic or inorganic polymer,preferably a homopolymer of ethylene or propylene and/or a copolymer ofethylene and a copolymerizable comonomer, and (2) a polymer according toany one of embodiments 5-7, or preparable by the method of embodiment 3or 4.

27. A polymer mixture according to embodiment 26 wherein component (1)is an organic thermoplastic polymer.

28. A polymer mixture according to embodiment 27 wherein component (1)is an ethylene or propylene homopolymers or a copolymer of ethylene anda C₃₋₈ α-olefin.

29. A polymer mixture according to embodiment 27 wherein component (2)is an elastomeric ethylene polymer.

The skilled artisan will appreciate that the invention disclosed hereinmay be practiced in the absence of any component, step or ingredientwhich has not been specifically disclosed.

EXAMPLES

The following examples are provided as further illustration of theinvention and are not to be construed as limiting. The term “overnight”,if used, refers to a time of approximately 16-18 hours, the term “roomtemperature”, refers to a temperature of 20-25° C., and the term “mixedalkanes” refers to a commercially obtained mixture of C₆₋₉ aliphatichydrocarbons available under the trade designation Isopar E®, from ExxonMobil Chemicals Inc. In the event the name of a compound herein does notconform to the structural representation thereof, the structuralrepresentation shall control. The synthesis of all metal complexes andthe preparation of all screening experiments were carried out in a drynitrogen atmosphere using dry box techniques. All solvents used wereHPLC grade and were dried before their use.

MMAO refers to modified methylalumoxane, a triisobutylaluminum modifiedmethylalumoxane available commercially from Akzo-Noble Corporation.

Catalyst (A1) is bis(indenyl)zirconium dimethyl.

Catalyst (B1) is:

prepared according to the teachings of Macromolecular Chemistry andPhysics, (2004), 205, 897-906.

Cocatalyst 1 A mixture of methyldi(C₁₄₋₁₈ alkyl)ammonium salts oftetrakis(pentafluorophenyl)borate (here-in-after armeenium borate),prepared by reaction of a long chain trialkylamine (Armeen™ M2HT,available from Akzo-Nobel, Inc.), HCl and Li[B(C₆F₅)₄], substantially asdisclosed in U.S. Pat. No. 5,919,9883, Ex. 2.

Shuttling Agents The shuttling agents employed are diethylzinc (DEZ)and, trioctylaluminum (TOA)

General High Throughput Parallel Polymerization Conditions

Polymerizations are conducted using a high throughput, parallelpolymerization reactor (PPR) available from Symyx technologies, Inc. andoperated substantially according to U.S. Pat. Nos. 6,248,540, 6,030,917,6,362,309, 6,306,658, and 6,316,663. Polymerizations are conducted at120° C. using 1.2 equivalents of cocatalyst 1 based on total catalystused. The polymerizations are conducted in a parallel pressure reactor(PPR) comprised of 48 individual reactor cells in a 6×8 array that arefitted with a pre-weighed glass tube. The working volume in each reactorcell is 6000 μL. Each cell is temperature and pressure controlled withstirring provided by individual stirring paddles. The monomer gas andquench gas are plumbed directly into the PPR unit and controlled byautomatic valves. Liquid reagents are robotically added to each reactorcell by syringes and the reservoir solvent is mixed alkanes. The orderof addition is mixed alkanes solvent (4 ml), ethylene, cocatalyst,shuttling agent, and catalyst. After quenching with CO, the reactors arecooled and the glass tubes are unloaded. The tubes are transferred to acentrifuge/vacuum drying unit, and dried for 12 hours at 60° C. Thetubes containing dried polymer are weighed and the difference betweenthis weight and the tare weight gives the net yield of polymer.

Example 1

A 6-mL reaction vessel containing a glass vial insert is charged withmixed alkanes (3.295 mL), and then pressurized to 200 psi (1.4 MPa) withethylene. Cocatalyst 1 (1.23 mM in toluene, 0.205 mL, 2.52 μmol) and DEZ(2.5 mM in toluene, 0.200 mL, 0.5 μmol) are sequentially added viasyringe. A mixture of catalyst A1 (1.0 mM in toluene, 0.10 mL, 100 nmol)and B1 (10 mM in toluene, 0.20 mL, 2.0 μmol) is added via syringe. After1200 seconds, the reaction is quenched by addition of CO. The glassinsert is removed and volatile components removed under vacuum. GPCanalysis shows PDI<2.0.

Example 2

A 6-mL reaction vessel containing a glass vial insert is charged withmixed alkanes (3.296 mL), and then pressurized to 200 psi (1.4 MPa) withethylene. Cocatalyst 1 (1.23 mM in toluene, 0.205 mL, 2.52 μmol) and TOA(2.5 mM in toluene, 0.200 mL, 0.5 μmol) are sequentially added viasyringe. A mixture of catalyst A1 (1.0 mM in toluene, 0.10 mL, 100 nmol)and B1 (10 mM in toluene, 0.20 mL, 2.0 μmol) is added via syringe. After1200 seconds, the reaction is quenched by addition of CO. The glassinsert is removed and volatile components removed under vacuum. GPCanalysis shows PDI<2.0.

Comparative A

A 6-mL reaction vessel containing a glass vial insert is charged withmixed alkanes (3.292 mL), and then pressurized to 200 psi (1.4 MPa) withethylene. Cocatalyst 1 (1.23 mM in toluene, 0.205 mL, 2.52 mmol) andMMAO (50 mM in toluene, 0.210 mL, 10.5 mmol) are sequentially added viasyringe. A mixture of catalysts A1 (1.0 mM in toluene, 0.10 mL, 100nmol) and B1 (10 mM in toluene, 0.20 mL, 2.0 mmol) is added via syringe.After 1200 seconds, the reaction is quenched by addition of CO. Theglass insert is removed and volatile components removed under vacuum.GPC analysis shows PDI>2.0.

Examples 1-2 demonstrate the synthesis of linear block copolymers by thepresent invention as evidenced by the formation of a very narrow MWD,essentially monomodal copolymer when DEZ or TOA is present and abimodal, broad molecular weight distribution product (a mixture oflinear and branched polyethylene polymers) in the absence of a chainshuttling agent (comparative A). Due to the fact that Catalyst (A1)produces polymer chains with different branching characteristics thanCatalyst (B1), the different blocks or segments of the resultingmulti-block copolymers are distinguishable based on branching frequency.

Continuous Solution Polymerization

Continuous solution polymerizations are carried out in a computercontrolled autoclave reactor equipped with an internal stirrer. Purifiedmixed alkanes solvent (Isopar™ E available from ExxonMobil, Inc.),ethylene, and hydrogen (where used) are supplied to a 3.8 L reactorequipped with ajacket for temperature control and an internalthermocouple. The solvent feed to the reactor is measured by a mass-flowcontroller. A variable speed diaphragm pump controls the solvent flowrate and pressure to the reactor. At the discharge of the pump, a sidestream is taken to provide flush flows for the catalyst and cocatalyst 1injection lines and the reactor agitator. These flows are measured byMicro-Motion mass flow meters and controlled by control valves or by themanual adjustment of needle valves. The remaining solvent is combinedwith ethylene and hydrogen (where used) and fed to the reactor. A massflow controller is used to deliver hydrogen to the reactor as needed.The temperature of the solvent/monomer solution is controlled by use ofa heat exchanger before entering the reactor. Temperature of the reactoris maintained at the desired temperature, typically between 70-170° C.This stream enters the bottom of the reactor. The catalyst componentsolutions are metered using pumps and mass flow meters and are combinedwith the catalyst flush solvent and introduced into the bottom of thereactor. The reactor is run liquid-full at 500 psig (3.45 MPa) withvigorous stirring. Product is removed through exit lines at the top ofthe reactor. All exit lines from the reactor are steam traced andinsulated. Polymerization is stopped by the addition of a small amountof water into the exit line along with any stabilizers or otheradditives and passing the mixture through a static mixer. The productstream is then heated by passing through a heat exchanger beforedevolatilization. The polymer product is recovered by extrusion using adevolatilizing extruder and water cooled pelletizer.

The reactor temperature and monomer concentration are used to controlthe composition or density of the polymer segment or block produced byeach catalyst, enabling production of polymer segments or blocks fromthe two catalysts that are distinguishable based on branching ordensity. Suitable blocks comprising linear polyethylene and branchedpolyethylene can be produced by achieving the correct ethyleneconcentration, catalyst ratios, and amount of chain shuttling agent(DEZ) added. Monomer conversion is regulated at the desired level byadjusting the feeds of the catalysts. The overall composition of thepolymer, meaning the amount of linear and branched polyethylene, iscontrolled by modifying either the catalyst feed ratio or the reactortemperature or monomer concentration. Hydrogen and/or DEZ is used tocontrol molecular weight of the polymer. When hydrogen alone is used forcontrol of molecular weight, the product can display bimodal molecularweight and composition distributions. This copolymer blend can beseparated by techniques commonly used by those skilled in the art.Conversely, when DEZ is used for molecular weight control, the copolymerdisplays narrow molecular weight and composition distributionsconsistent with a multi-block polymer.

The inventive polymer samples from the above continuous solutionpolymerization procedure can display several enhanced characteristicsrelative to comparative examples or linear or branched ethylenepolymers. For example, high temperature resistance properties, asevidenced by TMA temperature testing, pellet blocking strength, hightemperature recovery, high temperature compression set and storagemodulus ratio, G′(25° C.)/G′(100° C.), can all be achieved. At a givencomposition, the inventive copolymers can also display a high meltingtemperature, Tm, and a low glass transition temperature, Tg, withTm≧135° C., and Tg≦−40° C.

1. A composition comprising the admixture or reaction product resultingfrom combining: (A) a first olefin polymerization catalyst, (B) a secondolefin polymerization catalyst capable of preparing polymers differingin chemical or physical properties from the polymer prepared by catalyst(A) under equivalent polymerization conditions, at least one of catalyst(A) or catalyst (B) being capable of forming a branched polymer by meansof chain walking or reincorporation of in situ formed olefinic polymerchains, and (C) a chain shuttling agent.
 2. A composition comprising theadmixture or reaction product resulting from combining: (A) a firstolefin polymerization catalyst capable of forming a highly crystallineethylene homopolymers by ethylene polymerization; (B) a second olefinpolymerization catalyst capable of forming a branched polymer uponpolymerization by means of chain walking or reincorporation of in situformed olefinic polymer chains, and (C) a chain shuttling agent.
 3. Aprocess for preparing a high molecular weight, multi-block copolymercomprising contacting ethylene under addition polymerization conditionswith a composition comprising: the admixture or reaction productresulting from combining: (A) a first olefin polymerization catalyst,(B) a second olefin polymerization catalyst capable of preparingpolymers differing in chemical or physical properties from the polymerprepared by catalyst (A) under equivalent polymerization conditions, atleast one of catalyst (A) or catalyst (B) being capable of forming abranched polymer by means of chain walking or reincorporation of in situformed olefinic polymer chains, and (C) a chain shuttling agent.
 4. Aprocess for preparing a high molecular weight, multi-block copolymercomprising contacting ethylene under addition polymerization conditionswith a composition comprising: the admixture or reaction productresulting from combining: (A) a first olefin polymerization catalystcapable of forming a highly crystalline ethylene homopolymer by ethylenepolymerization; (B) a second olefin polymerization catalyst capable offorming a branched polymer upon polymerization by means of chain walkingor reincorporation of in situ formed olefinic polymer chains, and (C) achain shuttling agent.
 5. A multi-block copolymer formed from a reactionmixture consisting essentially of ethylene as the addition polymerizablemonomer, said copolymer containing therein two or more segments orblocks differing in branching index, said copolymer possessing amolecular weight distribution, Mw/Mn, of less than 3.0.
 6. A multi-blockcopolymer formed from a reaction mixture consisting essentially ofethylene as the addition polymerizable monomer, said copolymercontaining therein two or more segments or blocks differing in branchingindex.
 7. A multi-block copolymer according to claim 6 possessing amolecular weight distribution, Mw/Mn, of less than 3.0.
 8. Afunctionalized derivative of the multi-block copolymer of any one ofclaims 5-7.
 9. A crosslinked derivative of a polymer according to anyone of claims 5-7.
 10. A crosslinked derivative of a polymer accordingto claim
 8. 11. A polymer according to any one of claims 5-7, orpreparable by the method of claim 3 or 4, or a composition comprisingthe same in the form of a film, at least one layer of a multilayer film,at least one layer of a laminated article, a foamed article, a fiber, anonwoven fabric, an injection molded article, a blow molded article, aroto-molded article, or an adhesive.
 12. A polymer according to claim 8or a composition comprising the same in the form of a film, at least onelayer of a multilayer film, at least one layer of a laminated article, afoamed article, a fiber, a nonwoven fabric, an injection molded article,a blow molded article, a roto-molded article, or an adhesive.
 13. Apolymer according to claim 9 or a composition comprising the same in theform of a film, at least one layer of a multilayer film, at least onelayer of a laminated article, a foamed article, a fiber, a nonwovenfabric, an injection molded article, a blow molded article, aroto-molded article, or an adhesive.
 14. A polymer according to claim 10or a composition comprising the same in the form of a film, at least onelayer of a multilayer film, at least one layer of a laminated article, afoamed article, a fiber, a nonwoven fabric, an injection molded article,a blow molded article, a roto-molded article, or an adhesive.
 15. Acomposition according to claim 1 or 2 wherein the shuttling agent is atrihydrocarbyl aluminum- or dihydrocarbyl zinc-compound containing from1 to 12 carbons in each hydrocarbyl group.
 16. A composition accordingto claim 15 wherein the shuttling agent is triethylaluminum ordiethylzinc.
 17. A composition according to claim 1 or 2 whereincatalyst (A) comprises a complex comprising a transition metal selectedfrom Groups 4-8 of the Periodic Table of the Elements and one or moredelocalized, π-bonded ligands or polyvalent Lewis base ligands.
 18. Acomposition according to claim 17 wherein catalyst (A) corresponds tothe formula:

wherein: R¹¹ is selected from alkyl, cycloalkyl, heteroalkyl,cycloheteroalkyl, aryl, and inertly substituted derivatives thereofcontaining from 1 to 30 atoms not counting hydrogen or a divalentderivative thereof; T¹ is a divalent bridging group of from 1 to 41atoms other than hydrogen; and R¹² is a C₅₋₂₀ heteroaryl groupcontaining Lewis base functionality; M¹ is a Group 4 metal; X¹ is ananionic, neutral or dianionic ligand group; x′ is a number from 0 to 5indicating the number of such X¹ groups; and bonds, optional bonds andelectron donative interactions are represented by lines, dotted linesand arrows respectively.
 19. A composition according to claim 18 whereincatalyst (B) corresponds to the formula:

wherein M² is a metal of Groups 4-10 of the Periodic Table of theelements; T² is a nitrogen, oxygen or phosphorus containing group; X² ishalo, hydrocarbyl, or hydrocarbyloxy; t is one or two; x″ is a numberselected to provide charge balance; and T² and N are linked by abridging ligand.
 20. A process according to claim 3 or 4 which is acontinuous process.
 21. A process according to claim 20 which is asolution process.
 22. (canceled)
 22. A process according to claim 21wherein the ethylene conversion in the reactor is at least 95 percent.23. A process according to claim 20 wherein catalyst (A) corresponds tothe formula:

wherein: R¹¹ is selected from alkyl, cycloalkyl, heteroalkyl,cycloheteroalkyl, aryl, and inertly substituted derivatives thereofcontaining from 1 to 30 atoms not counting hydrogen or a divalentderivative thereof; T¹ is a divalent bridging group of from 1 to 41atoms other than hydrogen; and R¹² is a C₅₋₂₀ heteroaryl groupcontaining Lewis base functionality, especially a pyridin-2-yl- orsubstituted pyridin-2-yl group or a divalent derivative thereof; M¹ is aGroup 4 metal; X¹ is an anionic, neutral or dianionic ligand group; x′is a number from 0 to 5 indicating the number of such X¹ groups; andbonds, optional bonds and electron donative interactions are representedby lines, dotted lines and arrows respectively.
 24. A process accordingto claim 23 wherein catalyst (B) corresponds to the formula:

wherein M² is a metal of Groups 4-10 of the Periodic Table of theelements; T² is a nitrogen, oxygen or phosphorus containing group; X² ishalo, hydrocarbyl, or hydrocarbyloxy; t is one or two; x″ is a numberselected to provide charge balance; and T² and N are linked by abridging ligand.
 25. A process according to claim 3 or 4 in which theratio of chain shuttling agent to one or more catalysts and or monomersis varied in order to produce polymers differing in one or more chemicalor physical properties.
 26. A polymer mixture comprising: (1) an organicor inorganic polymer, and (2) a polymer according to any one of claims5-7, or preparable by the method of claim 3 or
 4. 27. A polymer mixtureaccording to claim 26 wherein component (1) is an organic thermoplasticpolymer.
 28. A polymer mixture according to claim 27 wherein component(1) is an ethylene or propylene homopolymers or a copolymer of ethyleneand a C₃₋₈ α-olefin.
 29. A polymer mixture according to claim 27 whereincomponent (2) is an elastomeric ethylene polymer.